Compositions including hardness ions and gluconate and methods employing them to reduce corrosion and etch

ABSTRACT

The present invention relates to compositions including a water soluble magnesium salt, water soluble calcium salt, and gluconate, which have a beneficial effect on corrosion during cleaning. The present compositions can reduce corrosion of glass, aluminum, or steel. The present invention also relates to methods employing these compositions.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application Ser.No. 60/927,575 filed on May 4, 2007 and entitled “CompositionsContaining Magnesium Salts and Methods of Using”, the disclosure ofwhich is incorporated herein by reference.

This application is also related to: U.S. patent application Ser. No.______, entitled “Cleaning Compositions with Water Insoluble ConversionAgents and Methods of Making and Using Them” (Attorney Docket No.2454US01); U.S. patent application Ser. No. ______, entitled,“Composition For In Situ Manufacture Of Insoluble Hydroxide WhenCleaning Hard Surfaces And For Use In Automatic Warewashing Machines,And Methods For Manufacturing And Using” (Attorney Docket No. 2437US01);U.S. patent application Ser. No. ______, entitled “Water TreatmentSystem and Downstream Cleaning Methods” (Attorney Docket No. 2428US01);U.S. patent application Ser. No. ______, entitled “Water SolubleMagnesium Compounds as Cleaning Agents and Methods of Using Them”(Attorney Docket No. 2372USU1); U.S. patent application Ser. No. ______,entitled “Cleaning Compositions Containing Water Soluble MagnesiumCompounds and Methods of Using Them” (Attorney Docket No. 2488US01);U.S. patent application Ser. No. ______, entitled “MG++ Chemistry andMethod for Fouling Inhibition in Heat Processing of Liquid Foods andIndustrial Processes” (Attorney Docket No. 2400US01); U.S. patentapplication Ser. No. ______, entitled “Compositions Including HardnessIon and Silicate and Methods Employing Them to Reduce Corrosion andEtch” (Attorney Docket No. 163.2487US01); U.S. patent application Ser.No. ______, entitled “Compositions Including Hardness Ion and ThresholdAgent and Methods Employing Them to Reduce Corrosion and Etch” (AttorneyDocket No. 163.2406US01); and U.S. patent application Ser. No. ______,entitled “Warewashing Compositions for Use in Automatic DishwashingMachines and Method for Using” (Attorney Docket No. 2378US01), allcommonly assigned to Ecolab, Inc., are filed on the same date as thisapplication being May 2, 2008 and are all incorporated herein byreference for all purposes.

FIELD OF THE INVENTION

The present invention relates to compositions including a water solublemagnesium salt, water soluble calcium salt, and gluconate, which have abeneficial effect on corrosion during cleaning. The present compositionscan reduce corrosion of glass, aluminum, or steel. The present inventionalso relates to methods employing these compositions.

BACKGROUND OF THE INVENTION

Hard water can cause stains on articles as a result of a visible filmdepositing onto the surface of the articles. The film may be caused bycalcium present in hard water precipitating and depositing onto thesurface. To prevent such precipitation, cleaning compositions caninclude a chelating agent.

In some circumstances, precipitation of calcium salts can be beneficial.Etching or corrosion of glass or aluminum is a common problem inwarewashing and surface cleaning. Glassware that is repetitively washedin automatic dishwashing machines has a tendency to develop an etchingproblem as evidenced by a surface cloudiness that is irreversible. Thecloudiness can manifest itself as an iridescent film that displaysrainbow hues in light reflected from the glass surface. The glassbecomes progressively more opaque with repeated washings. It is believedthat the glassware corrosion problem relates to two separate phenomena;the first is corrosion or etching due to the leaching out of mineralsfrom the glass composition itself together with hydrolysis of thesilicate network, and the second is chelation of ions contained in theglass by the detergent's builder.

Common corrosion inhibitors work by causing controlled precipitation ofcalcium salts, which can reduce such etching or corrosion. Calciumgluconate is one such corrosion inhibitor. However, calcium gluconatecan produce undesirable scale or deposits on the object to be cleaned.

It is counterintuitive to include a second hardness ion (e.g., magnesiumion) with calcium gluconate to achieve a corrosion inhibitor which doesnot cause scaling as an undesirable side-effect.

SUMMARY OF THE INVENTION

Unexpectedly, the present inventors have developed compositions thatsynergistically reduce corrosion of glass and aluminum. The synergisticcompositions include defined ratios of water soluble calcium salt, watersoluble magnesium salt, and gluconate that do not leave visible scale onsurfaces. Synergy was determined from the data obtained from designedexperiments and an analysis specifically focused on finding synergy.Ratios of ingredients that achieve synergy include:

Water soluble 1-2:1-2 1-1.50:1-1.50 1-1.25:1-1.25 1:1 calcium salt towater soluble magnesium salt Water soluble 1:1 or 1.25:1 or 1.5:1 or 2:1or magnesium salt to greater greater greater greater gluconate Watersoluble 1-19:1-13 1-15:1-8  3-10:1-5  3-8:2-4 calcium salt to gluconateCombinations of these ratios of ingredients also result in synergy. Anillustrative combination of ratios is a composition that includes aweight ratio of 1-2:2-1 for water soluble calcium salt to water solublemagnesium salt; weight ratio of 1:1 or greater of water solublemagnesium salt to gluconate; and a weight ratio of 1-19:1-13 for watersoluble calcium salt to gluconate. The present invention includescorrosion inhibitor compositions including water soluble calcium salt,water soluble magnesium salt, and gluconate; cleaning compositionsincluding the corrosion inhibitor; and methods of cleaning and reducingcorrosion.

In an embodiment, the present invention relates to a corrosioninhibiting composition. The corrosion inhibitor can include watersoluble calcium salt, water soluble magnesium salt, and gluconate. Thecomposition can include about 1 to about 98 wt-% water soluble calciumsalt and water soluble magnesium salt and about 1 to about 60 wt-%gluconate. In the composition, the weight ratio of water solublemagnesium salt to water soluble calcium salt can be about 1-2:1-2; theweight ratio of water soluble magnesium salt to gluconate can be greaterthan 1:1; and the weight ratio of water soluble calcium salt togluconate can be about 1-19:1:13.

In an embodiment, the present invention relates to a cleaningcomposition including the present corrosion inhibitor. The cleaningcomposition can be a detergent for warewashing or automatic dishwashing.This detergent can include source of alkalinity and about 0.01 to about20 wt-% of the present corrosion inhibitor. The cleaning composition canbe a hard surface cleaner. This hard surface cleaner can include sourceof alkalinity and about 0.01 to about 20 wt-% of the present corrosioninhibitor.

In an embodiment, the present invention relates to a method employingthe present corrosion inhibitor or the present cleaning composition. Themethod can include providing the present corrosion inhibitor or thepresent cleaning composition. The method can include preparing anaqueous use composition of the present corrosion inhibitor or thepresent cleaning composition. The method includes contacting an object,such as ware or a hard surface, in need of cleaning with the aqueous usecomposition.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows data from Example 1 in the form of a ternary graphillustrating the reduced corrosion of the aluminum as a function of theconcentrations of magnesium chloride, calcium chloride, and sodiumgluconate. The synergistic interaction of select ratios of these threecomponents gave reduced aluminum dissolved from aluminum test couponswithout the formation of visible scale on the aluminum surface.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein, the term “water soluble” refers to a compound that canbe dissolved in water at a concentration of more than 1 wt-%.

As used herein, the terms “sparingly soluble” or “sparingly watersoluble” refer to a compound that can be dissolved in water only to aconcentration of 0.1 to 1.0 wt-%.

As used herein, the term “water insoluble” refers to a compound that canbe dissolved in water only to a concentration of less than 0.1 wt-%.

As used herein, the terms “chelating agent” and “sequestrant” refer to acompound that forms a complex (soluble or not) with water hardness ions(from the wash water, soil and substrates being washed) in a specificmolar ratio. Chelating agents that can form a water soluble complexinclude sodium tripolyphosphate, EDTA, DTPA, NTA, citrate, and the like.Sequestrants that can form an insoluble complex include sodiumtriphosphate, zeolite A, and the like. As used herein, the terms“chelating agent” and “sequestrant” are synonymous.

As used herein, the term “threshold agent” refers to a compound thatinhibits crystallization of water hardness ions from solution, but thatneed not form a specific complex with the water hardness ion. Thisdistinguishes a threshold agent from a chelating agent or sequestrant.Threshold agents include a polyacrylate, a polymethacrylate, anolefin/maleic copolymer, and the like.

As used herein, the term “antiredeposition agent” refers to a compoundthat helps keep suspended in water instead of redepositing onto theobject being cleaned.

As used herein, the term “phosphate-free” refers to a composition,mixture, or ingredient that does not contain a phosphate orphosphate-containing compound or to which a phosphate orphosphate-containing compound has not been added. Should a phosphate orphosphate-containing compound be present through contamination of aphosphate-free composition, mixture, or ingredients, the amount ofphosphate shall be less than 0.5 wt %. In an embodiment, the amount ofphosphate is less then 0.1 wt-%. In an embodiment, the amount ofphosphate is less than 0.01 wt %.

As used herein, the term “phosphorus-free” refers to a composition,mixture, or ingredient that does not contain phosphorus or aphosphorus-containing compound or to which phosphorus or aphosphorus-containing compound has not been added. Should phosphorus ora phosphorus-containing compound be present through contamination of aphosphorus-free composition, mixture, or ingredients, the amount ofphosphorus shall be less than 0.5 wt %. In an embodiment, the amount ofphosphorus is less than 0.1 wt-%. In an embodiment, the amount ofphosphorus is less than 0.01 wt %.

“Cleaning” means to perform or aid in soil removal, bleaching, microbialpopulation reduction, or combination thereof.

As used herein, the term “ware” includes items such as eating andcooking utensils. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware.

As used herein, the term “hard surface” includes showers, sinks,toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, floors, and the like.

As used herein, the phrase “health care surface” refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, or the like that is employed as part of a health careactivity. Examples of health care surfaces include surfaces of medicalor dental instruments, of medical or dental devices, of electronicapparatus employed for monitoring patient health, and of floors, walls,or fixtures of structures in which health care occurs. Health caresurfaces are found in hospital, surgical, infirmity, birthing, mortuary,and clinical diagnosis rooms. These surfaces can be those typified as“hard surfaces” (such as walls, floors, bed-pans, etc.,), or fabricsurfaces, e.g., knit, woven, and non-woven surfaces (such as surgicalgarments, draperies, bed linens, bandages, etc.,), or patient-careequipment (such as respirators, diagnostic equipment, shunts, bodyscopes, wheel chairs, beds, etc.,), or surgical and diagnosticequipment. Health care surfaces include articles and surfaces employedin animal health care.

As used herein, the term “instrument” refers to the various medical ordental instruments or devices that can benefit from cleaning with astabilized composition according to the present invention.

As used herein, the phrases “medical instrument”, “dental instrument”,“medical device”, “dental device”, “medical equipment”, or “dentalequipment” refer to instruments, devices, tools, appliances, apparatus,and equipment used in medicine or dentistry. Such instruments, devices,and equipment can be cold sterilized, soaked or washed and then heatsterilized, or otherwise benefit from cleaning in a composition of thepresent invention. These various instruments, devices and equipmentinclude, but are not limited to: diagnostic instruments, trays, pans,holders, racks, forceps, scissors, shears, saws (e.g. bone saws andtheir blades), hemostats, knives, chisels, rongeurs, files, nippers,drills, drill bits, rasps, burrs, spreaders, breakers, elevators,clamps, needle holders, carriers, clips, hooks, gouges, curettes,retractors, straightener, punches, extractors, scoops, keratomes,spatulas, expressors, trocars, dilators, cages, glassware, tubing,catheters, cannulas, plugs, stents, scopes (e.g., endoscopes,stethoscopes, and arthoscopes) and related equipment, and the like, orcombinations thereof.

As used herein, a solid cleaning composition refers to a cleaningcomposition in the form of a solid such as a powder, a flake, a granule,a pellet, a tablet, a lozenge, a puck, a briquette, a brick, a solidblock, a unit dose, or another solid form known to those of skill in theart. The term “solid” refers to the state of the detergent compositionunder the expected conditions of storage and use of the solid detergentcomposition. In general, it is expected that the detergent compositionwill remain in solid form when exposed to temperatures of up to about100° F. and greater than about 120° F.

By the term “solid” as used to describe the processed composition, it ismeant that the hardened composition will not flow perceptibly and willsubstantially retain its shape under moderate stress or pressure or meregravity, as for example, the shape of a mold when removed from the mold,the shape of an article as formed upon extrusion from an extruder, andthe like. The degree of hardness of the solid cast composition can rangefrom that of a fused solid block which is relatively dense and hard, forexample, like concrete, to a consistency characterized as beingmalleable and sponge-like, similar to caulking material.

As used herein, the term “organic component used in cell culture media”refers to sugars (e.g., glucose or dextrose), amino acids, vitamins,cofactors, pyruvate, organic buffers, fatty acids, and nucleosides thatare employed in cell culture media to nourish cells and provide themenergy for growth. The ATCC (American Type Culture Collection) cataloglists cell culture media including Dulbecco's Modified Eagle's Medium(DMEM), variants of DMEM (e.g., ES-DMEM, DMEM: F12 medium), Eagle'sMinimum Essential Medium (EMEM), F-12K Medium, Hybri-Care Medium,Iscove's Modified Dulbecco's Medium (IMDM), Leibovitz's L-15 Medium,McCoy's 5A Medium, RPMI-1640 Medium and provides lists of ingredientsand the amounts of ingredients in these media. These media are standardswhose contents are known. The content of these media is herebyincorporated by reference. In an embodiment, the present composition ifsubstantially free of any organic component of cell culture media. In anembodiment, the present composition is free of any organic component ofcell culture media.

As used herein, weight percent (wt-%), percent by weight, % by weight,and the like are synonyms that refer to the concentration of a substanceas the weight of that substance divided by the total weight of thecomposition and multiplied by 100.

As used herein, the term “about” modifying the quantity of an ingredientin the compositions of the invention or employed in the methods of theinvention refers to variation in the numerical quantity that can occur,for example, through typical measuring and liquid handling proceduresused for making concentrates or use solutions in the real world; throughinadvertent error in these procedures; through differences in themanufacture, source, or purity of the ingredients employed to make thecompositions or carry out the methods; and the like. Whether or notmodified by the term “about”, the claims include equivalents to thequantities.

Calcium Magnesium Gluconate Composition

The present inventors have unexpectedly discovered that compositionsincluding water soluble magnesium salt, water soluble calcium salt, andgluconate reduce corrosion during cleaning of, for example, articles ofglass, porcelain, ceramic, aluminum, or steel with alkaline cleaners.The compositions even synergistically reduced corrosion of aluminum. Thesynergistic compositions include defined ratios of water soluble calciumsalt, water soluble magnesium salt, and gluconate. Ratios of ingredientsthat achieve synergy are shown in Table A.

TABLE A Synergistic Weight Ratios Water soluble 1-2:1-2 1-1.50:1-1.501-1.25:1-1.25 1:1 calcium salt to water soluble magnesium salt Watersoluble 1:1 or 1.25:1 or 1.5:1 or greater 2:1 or magnesium greatergreater greater salt to gluconate Water soluble 1-19:1-13 1-15:1-8 3-10:1-5  3-8:2-4 calcium salt to gluconate Water soluble 4-7:1-35-6:1-2 5.2-5.8:1.2-1.8 11:3  calcium salt to gluconateBy “or greater” is meant that the number presented first in the ratiocan increase. For example, 1:1 or greater includes 2:1, 3:1, 1.1:1,1.2:1, and so on. The present invention also includes the amounts andranges stated in the tables modified by the word “about”.

Various combinations of water soluble magnesium salt, water solublecalcium salt, and water soluble gluconate salt were evaluated asprotectants for aluminum as described in Example 1 with results reportedas the ppm of aluminum dissolved in solution from an aluminum testcoupon. The data clearly shows synergistic ratios of the threecomponents which was synergistic, using as the definition of synergy aperformance better than any individual component, and which alsoprotected the aluminum better than any binary combination of components,including the calcium gluconate system known to be a corrosioninhibiter. Further, no scaling was observed for the synergistic areaswhich corresponded to the ratios in Table A.

Compositions of the invention can include amounts of water solublemagnesium salt, water soluble calcium salt, and gluconate shown in TableB.

TABLE B Concentrate Corrosion Inhibitor Composition by Wt-% Watersoluble magnesium salt 5-98 10-95  25-95  30-75 Water soluble calciumsalt 1-94 2-85 1-65 15-50 Gluconate 1-60 2-50 1-35  1-25The amounts of each ingredient can be selected to achieve the ratioslisted in Table A. For example, a composition that includes 10 wt-%gluconate can include 20 wt-% water soluble magnesium salt and 20 wt-%water soluble calcium salt, which provides a weight ratio of watersoluble calcium salt to water soluble magnesium salt of 1:1, a weightratio of water soluble magnesium salt to gluconate of 2:1, and a weightratio of water soluble calcium salt to gluconate of 2:1. Each of thesevalues is listed in or falls within a range listed in Table A. Forexample, a synergistic combination of the three components can include15-50% water soluble calcium salt, 30-75% water soluble magnesium salt,and 1-25% gluconate at the appropriate ratios.

The present corrosion inhibitor can include only water soluble calciumsalt, water soluble magnesium salt, and gluconate in the amounts andratios listed in Tables A and B. Alternatively, the present corrosioninhibitor can be part of a composition that also includes additionalingredient(s), in which case the amounts of ingredients selected fromTable B need not add up to 100 wt-%, the remainder can be any additionalingredient(s). The present invention also includes the amounts andranges stated in the tables modified by the word “about”.

The present invention relates to a cleaning composition including thepresent corrosion inhibitor composition and to methods employing thecleaning composition. This composition can include surfactant,alkalinity source, and sufficient water soluble magnesium salt, watersoluble calcium salt, and water soluble gluconate salt to providecorrosion/etch resistance without scale formation in the use solution.The present cleaning composition can include surfactant, alkalinitysource and the present corrosion inhibitor in amounts shown in Table C.

TABLE C Concentrate Cleaning Composition by Wt-% Surfactant 0.1-20 1-152-10 3-8 Alkalinity Source 0.1-70 1-50 2-40  5-30 Corrosion Inhibitor0.01-20  0.1-15   0.2-10   0.3-8  The present cleaning composition can also include additionalingredients, in which case the amounts of ingredients selected fromTable C need not add up to 100 wt-%, the remainder can be any additionalingredient(s). The corrosion inhibitor can be used in any applicationwhere it is desirable to reduce surface corrosion, such as in adetergent composition. The present invention also includes the amountsand ranges stated in the tables modified by the word “about”.

In an embodiment, the present invention relates to a composition andit's use for corrosion and/or etch control which is substantially freeof (or even free of) common detergent components. In an embodiment, thepresent corrosion inhibitor provided substantially free of (or even freeof) surfactant, alkalinity source, or builder. This composition caninclude sufficient water soluble magnesium salt, water soluble calciumsalt, and water soluble gluconate salt to provide corrosion/etchresistance without scale formation in the use solution. Such a corrosioninhibitor composition can be employed alone or, at the locus of use, thecorrosion inhibitor or use composition of the corrosion inhibitor can beemployed or combined with a separate cleaning composition known to thoseskilled in the art.

In certain embodiments, the present composition consists essentially ofwater soluble magnesium salt, water soluble calcium salt, and gluconate.As used herein, the phrases “consisting essentially of” or “consistsessentially of” refer to a composition including the listed ingredients(e.g., water soluble magnesium salt, water soluble calcium salt, andgluconate) but lacking an effective amount of any cleaning componentcommonly used in cleaning compositions.

In an embodiment, the present composition is free of cleaning componentscommonly used in cleaning compositions. As used herein, the phrase “freeof cleaning components commonly used in cleaning compositions” refers toa composition, mixture, or ingredient that does not contain a cleaningcomponent commonly used in cleaning compositions or to which a cleaningcomponent commonly used in a cleaning composition has not been added.Should a cleaning component commonly used in cleaning compositions bepresent through contamination of a composition free of cleaningcomponents commonly used in cleaning, the amount of cleaning componentcommonly used in cleaning compositions shall be less than 0.5 wt %. Inan embodiment, the amount of cleaning component commonly used incleaning compositions is less then 0.1 wt-%. In an embodiment, theamount of cleaning component commonly used in cleaning compositions isless than 0.01 wt %.

As used herein, “cleaning component commonly used in cleaningcompositions” refers to: source of alkalinity, organic surfactant orcleaning agent (e.g., surfactant or surfactant system, e.g., anionic,nonionic, cationic, and zwitterionic surfactant), pH modifier (e.g.,organic or inorganic source of alkalinity or a pH buffering agent),builder (e.g., inorganic builder such as silicate, carbonate, sulfate,salt or acid form thereof), processing aid, active oxygen compound,glass or metal corrosion inhibitor, activator, rinse aid functionalmaterial, bleaching agent, defoaming agent, anti-redeposition agent,stabilizing agent, enzyme, chelating agent or sequestrant (e.g.,phosphonate, phosphate, aminocarboxylate, polycarboxylate, and thelike), detersive polymer, softener, source of acidity, solubilitymodifier, bleaching agent or additional bleaching agent, effervescentagent, and activator for the source of alkalinity.

The water soluble magnesium salt, water soluble calcium salt, and watersoluble gluconate salt are sufficiently water-soluble so that when thecomposition is combined with a diluent, such as water, the compoundsdissolve. In this context, sufficiently water-soluble means that thesalts dissolve at a relatively quick rate in water. In an embodiment,the solubility of the water soluble magnesium salt, water solublecalcium salt, and water soluble gluconate salt is at least about 0.5wt-% in water at about 20° C. and atmospheric pressure. In anembodiment, the water soluble magnesium salt, water soluble calciumsalt, and water soluble gluconate salt remain soluble in solution. In anembodiment, the water soluble magnesium salt, water soluble calciumsalt, and water soluble gluconate salt remain dispersed in solution. Inan embodiment, once solubilized, the water soluble magnesium salt, watersoluble calcium salt, and water soluble gluconate salt interact to forma salt having limited water solubility (e.g., even water insoluble). Inthis context, the phrase “limited water solubility” means that the salthas a tendency to precipitate from the solution. In an embodiment, asalt having limited water solubility has a solubility of less than about0.5 wt-% in water at about 20° C. and atmospheric pressure.

The water-insoluble salt may be formed in-situ when the diluent is addedto the present composition or may be added to a liquid as a premadecomplex. Forming the water insoluble salt in situ can result in its morehomogeneous dispersion in solution. Forming the water insoluble salt asa premade complex can allow use of lower concentrations while achievingthe same level of effectiveness as forming the corrosion inhibitor insitu.

Theories of Operation

Although not limiting to the present invention, it is believed that, incertain embodiments, a salt formed from the hardness ions (e.g.,magnesium and calcium) and the gluconate forms a microscopic protectivefilm on the surface of articles exposed to the present composition. Theprotective film can be transparent or not visible to the unaided eye.Such as film can function as a protective layer to slow or prevent othercomponents that may be present in solution from attacking and corrodingthe surface of the article. Thus, the film functions as a sacrificiallayer and allows other components such as alkalinity sources, builders,or sequestrants, to attack and remove portions of the film, rather thanattack the surface of the article. A relatively thin film that may beeasily removed from the surface during subsequent cleaning so that a newfilm may be deposited on the surface to provide a new protective layer.Thus, it does not permanently build up on the surface and form aniridescent film or surface cloudiness. As a result, the precipitate filmis available to protect the surface but can be removed and regenerated.

Although not limiting to the present invention, it is believed that, incertain embodiments, the corrosion inhibitor protects the surface byreplacing ions extracted from the surface by an alkalinity source orbuilder in solution and/or by annealing the surface to remove surfacehydroxyl groups. The protective film can degrade during subsequent washcycles and can be continually regenerated as a result of precipitationof the salt

Although not limiting to the present invention, it is believed that, incertain embodiments, the rate of deposition of the salt is largelydependent on the ratio of total cations to anions and also the ratio ofmagnesium ion to calcium ion provided in the present composition. It isbelieved that these ratios may be manipulated such that the filmdeposited onto the surface is thick enough to protect against etchingbut is thin enough that it is relatively transparent and/or andsubstantially invisible to the naked eye such as by an individualcasually inspecting the glass in normal use situations (e.g., at adinner table). In selecting the ratio of cations to anions, numerousfactors can be considered, including, but not limited to: the hardnesslevel of the water, the cation source, the anion source, and thematerial of the surface to be protected.

Although not limiting to the present invention, it is believed that, incertain embodiments, it is believed that magnesium ions moderate theprecipitation/film formation of calcium gluconate such that theprotection layer does not build-up to the extent to which it is visibleto the unaided eye, i.e. does not build-up as scale.

Water Soluble Magnesium Salts

Suitable water soluble magnesium compounds include those selected fromthe group consisting of magnesium acetate, magnesium benzoate, magnesiumbromide, magnesium bromate, magnesium chlorate, magnesium chloride,magnesium chromate, magnesium citrate, magnesium formate, magnesiumhexafluorosilicate, magnesium iodate, magnesium iodide, magnesiumlactate, magnesium molybdate, magnesium nitrate, magnesium perchlorate,magnesium phosphinate, magnesium salicylate, magnesium sulfate,magnesium sulfite, magnesium thiosulfate, a hydrate thereof, and amixture thereof. These salts can be provided as hydrated salts oranhydrous salts.

Water soluble magnesium compounds approved as GRAS for direct foodcontact include magnesium chloride and magnesium sulfate.

Water Soluble Calcium Salts

Suitable water soluble calcium salts include those selected from thegroup consisting of calcium acetate, calcium benzoate, calcium bromate,calcium bromide, calcium chlorate, calcium chloride, calcium chromate,calcium dihydrogen phosphate, calcium dithionate, calcium formate,calcium gluconate, calcium glycerophosphate, calcium hydrogen sulfide,calcium iodide, calcium lactate, calcium metasilicate, calcium nitrate,calcium nitrite, calcium pantothenate, calcium perchlorate, calciumpermanganate, calcium phosphate, calcium phosphinate, calciumsalicylate, calcium succinate, a hydrate thereof, and a mixture thereof.These salts can be provided as hydrated compounds or anhydrouscompounds.

Gluconate

Gluconate is the salt of gluconic acid. Water soluble gluconate salts,e.g., sodium gluconate are commercially available. Additionalcommercially available forms of gluconate include potassium gluconate,lithium gluconate, and magnesium gluconate.

Water

Water can be hard water, city water, well water, water supplied by amunicipal water system, water supplied by a private water system,treated water, or water directly from the system or well. In general,hard water refers to water having a level of calcium and magnesium ionsin excess of about 100 ppm. Often, the molar ratio of calcium tomagnesium in hard water is about 2:1 or about 3:1. Although mostlocations have hard water, water hardness tends to vary from onelocation to another. Water can be potable water as obtained from amunicipal or private water system, e.g., a public water supply or awell.

Embodiments of the Present Compositions

The present calcium magnesium gluconate composition can be provided inany of a variety of embodiments of compositions. For example, thecalcium magnesium gluconate composition can be a component of a cleaningcomposition. Such a cleaning composition can include calcium magnesiumgluconate composition, surfactant, and alkalinity source.

In an embodiment, the present composition is substantially free of zinc.In general, the present composition can be characterized assubstantially free of zinc if the corrosion inhibitor contains nointentionally added zinc. For example, the present composition may becharacterized as substantially free of zinc if it contains no zinc, orif zinc is present, the amount of zinc is less than about 0.01 wt-%.Zinc can unnecessarily consume certain builders or chelating agents,which is a reason to exclude it.

In an embodiment, the present composition does not include phosphorus ornitrilotriacetic acid (NTA) containing compounds. Phosphorus-free refersto a composition, mixture, or ingredients to which phosphorus-containingcompounds are not added. Should phosphorus-containing compounds bepresent, the level of phosphorus-containing compounds in the resultingcomposition should be less than about 1 wt-%, less than about 0.5 wt-%,less than about 0.1 wt-%, or less than about 0.01 wt-%. NTA-free refersto a composition, mixture, or ingredients to which NTA-containingcompounds are not added. Should NTA-containing compounds be present, thelevel of NTA in the resulting composition should be less than about 1wt-%, less than about 0.5 wt-%, less than about 0.1 wt-%, or less thanabout 0.01 wt-%. When the detergent composition is NTA-free, thedetergent composition is also compatible with chlorine, which functionsas an anti-redeposition and stain-removal agent.

In an embodiment, the present composition includes a source of hardnessions (e.g., magnesium and calcium ions) and a gluconate that arecharacterized by the United States Food and Drug Administration asdirect or indirect food additives.

Warewashing Composition

The present calcium magnesium gluconate composition can be employed as acomponent of a warewashing composition. Warewashing can etch wares madeof, for example, aluminum, glass, ceramic, or porcelain. Table Ddescribes ingredients for suitable warewashing compositions. The presentinvention also includes the amounts and ranges stated in the tablesmodified by the word “about”.

TABLE D Warewashing Compositions Warewashing Warewashing Composition 1Composition 2 Ingredient (wt-%) (wt-%) Calcium Magnesium Gluconate0.01-20  0.1-10  Composition alkaline source   5-60 10-50 surfactant0.05-20  0.5-15  builder   1-60  3-50 water 0.1-60 Optional Ingredients:bleaching agent 0.1-60  1-20 filler   1-20  3-15 defoaming agent 0.01-3 0.1-2   anti-deposition agent 0.5-10 1-5 stabilizing agent 0.5-15  2-10dispersant 0.5-15 2-9 enzyme 0.5-10 1-5

The present composition can be a warewashing composition. Thewarewashing detergent composition includes a cleaning agent, an alkalinesource, and a corrosion inhibitor. The cleaning agent comprises adetersive amount of a surfactant. The alkaline source is provided in anamount effect to provide a use composition having a pH of at least about8 when measured at a concentration of about 0.5 wt. %. The corrosioninhibitor can be provided in an amount sufficient for reducing corrosionof glass, porcelain, ceramic, or aluminum when the warewashing detergentcomposition is combined with water of dilution at a dilution ratio ofdilution water to detergent composition of at least about 20:1. A methodfor using a warewashing detergent composition is provided according tothe invention. The method includes steps of diluting the warewashingdetergent composition with water of dilution at a ratio of waterdilution to warewashing detergent composition of at least about 20:1,and washing glass with the use composition in an automatic dishwashingmachine.

The warewashing composition, can be available for cleaning inenvironments other than inside an automatic dishwashing or warewashingmachine. For example, the composition can be used as a pot and pancleaner for cleaning glass, dishes, etc. in a sink. The warewashingcomposition includes an effective amount of a corrosion inhibitor toprovide a use composition exhibiting resistance to glass corrosion. Thephrase “effective amount” in reference to the corrosion inhibitor refersto an amount sufficient to provide a use composition exhibiting reducedglass corrosion compared with a composition that is identical exceptthat it does not contain a sufficient amount of the corrosion inhibitorto reduce corrosion of glass after multiple washings.

The warewashing composition prior to dilution to provide the usecomposition can be referred to as the warewashing compositionconcentrate or more simply as the concentrate. The concentrate can beprovided in various forms including as a liquid or as a solid. Pastesand gels can be considered types of liquid. Powders, agglomerates,pellets, tablets, and blocks can be considered types of solid.

Hard Surface Cleaner

The present calcium magnesium gluconate composition can be employed as acomponent of a hard surface cleaning composition. Hard surface cleanerscan etch objects made of, for example, aluminum or glass. Table Edescribes ingredients for suitable hard surface cleaners. The presentinvention also includes the amounts and ranges stated in the tablesmodified by the word “about”.

TABLE E Hard Surface Cleaning Compositions Hard Surface Hard SurfaceHard Surface Cleaner 1 Cleaner 2 Cleaner 3 Ingredient (wt-%) (wt-%)(wt-%) Calcium Magnesium 0.01-20   0.1-10 0.2-8 Gluconate Compositionnonionic surfactant 0.01-20   0.1-15 0.5-8 Optional Ingredients: anionicsurfactant 0-20 0.1-15 0.5-8 amphoteric surfactant 0-10 0.1-8  0.5-5non-phosphorus containing 0.01-30   0.1-25   1-15 builderanti-redeposition agent 0-10 0.1-8  0.3-5 alkalinity source 0.1-30  0.5-25   1-15 thickener 0-5  0.1-4  0.5-3 organic solvent 0-20 0.1-15 0.5-10 antimicrobial agent 0-20 0.01-15  0.03-10 solidification agent5-90  10-80   20-60 water balance balance balance Hard Surface HardSurface Hard Surface Cleaner 4 Cleaner 5 Cleaner 6 Ingredient (wt-%)(wt-%) (wt-%) Calcium Magnesium 0.3-6   0.4-5  0.5-4 GluconateComposition nonionic surfactant 0.01-20   0.1-15 0.5-8 OptionalIngredients: anionic surfactant 0-20 0.1-15 0.5-8 amphoteric surfactant0-10 0.1-8  0.5-5 non-P containing builder 0.01-30   0.1-25   1-15anti-redeposition agent 0-10 0.1-8  0.3-5 alkalinity source 0.1-30  0.5-25   1-15 thickener 0-5  0.1-4  0.5-3 organic solvent 0-20 0.1-15 0.5-10 antimicrobial agent 0-20 0.01-15  0.03-10 water balance balancebalance

A hard surface cleaner can be configured to be diluted with water toprovide a use composition that can be used to clean hard surfaces.Examples of hard surfaces include, but are not limited to: architecturalsurfaces such as walls, showers, floors, sinks, mirrors, windows, andcountertops; transportation vehicles such as cars, trucks, buses,trains, and planes; surgical or dental instruments; food processingequipment; and washing equipment such as dishwashers or laundrymachines.

Solid Cleaning Compositions

The present calcium magnesium gluconate composition can be employed as acomponent of a solid cleaning composition. Solid cleaning compositioncan etch objects made of, for example, aluminum, glass, ceramic, orporcelain. Table F describes ingredients for solid cleaningcompositions. The present invention also includes the amounts and rangesstated in the tables modified by the word “about”.

TABLE F Solid Cleaning Compositions Solid Cleaning Solid CleaningComposition 1 Composition 2 Ingredient (wt-%) (wt-%) Calcium Magnesium0.01-20  0.1-10   Gluconate Composition Surfactant 0.1-40 1-20 alkalinesource  10-80 15-70  solidifying agent 0.1-80 1-60 water   0-50 0.1-30  binding agent 0.1-80 1-60

Additional Ingredients

Solid cleaning compositions made according to the invention may furtherinclude additional functional materials or additives that provide abeneficial property, for example, to the composition in solid form orwhen dispersed or dissolved in an aqueous solution, e.g., for aparticular use. Examples of conventional additives include one or moreof each of polymer, surfactant, secondary hardening agent, solubilitymodifier, detergent filler, defoamer, anti-redeposition agent,antimicrobial, aesthetic enhancing agent (i.e., dye, odorant, perfume),optical brightener, bleaching agent or additional bleaching agent,enzyme, effervescent agent, activator for the source of alkalinity, andmixtures thereof.

Builder

In an embodiment, the present composition includes a builder that isincapable of chelating a significant amount of or any of the magnesium.Zeolite 3A is an example of this type of builder. A purpose of suchbuilder can be to increase the molar ratio of Mg/Ca in the use solution.This can reduce the amount of magnesium compound used as an ingredientin the solid composition.

Organic Surfactants or Cleaning Agents

The composition can include at least one cleaning agent which can be asurfactant or surfactant system. A variety of surfactants can be used ina cleaning composition, including anionic, nonionic, cationic, andzwitterionic surfactants, which are commercially available from a numberof sources. Suitable surfactants include nonionic surfactants. Suitablenonionic surfactants include low foaming non-ionic surfactants. For adiscussion of surfactants, see Kirk-Othmer, Encyclopedia of ChemicalTechnology, Third Edition, volume 8, pages 900-912.

Nonionic surfactants are useful in the present solid compositions,include those having a polyalkylene oxide polymer as a portion of thesurfactant molecule. Such nonionic surfactants include, for example,chlorine-, benzyl-, methyl-, ethyl-, propyl-, butyl- and other likealkyl-capped polyethylene and/or polypropylene glycol ethers of fattyalcohols; polyalkylene oxide free nonionics such as alkylpolyglycosides; sorbitan and sucrose esters and their ethoxylates;alkoxylated ethylene diamine; carboxylic acid esters such as glycerolesters, polyoxyethylene esters, ethoxylated and glycol esters of fattyacids, and the like; carboxylic amides such as diethanolaminecondensates, monoalkanolamine condensates, polyoxyethylene fatty acidamides, and the like; and ethoxylated amines and ether aminescommercially available from Tomah Corporation and other like nonioniccompounds. Silicone surfactants such as the ABIL B8852 (Goldschmidt) canalso be used.

Additional suitable nonionic surfactants having a polyalkylene oxidepolymer portion include nonionic surfactants of C6-C24 alcoholethoxylates (e.g., C6-C14 alcohol ethoxylates) having 1 to about 20ethylene oxide groups (e.g., about 9 to about 20 ethylene oxide groups);C6-C24 alkylphenol ethoxylates (e.g., C8-C10 alkylphenol ethoxylates)having 1 to about 100 ethylene oxide groups (e.g., about 12 to about 20ethylene oxide groups); C6-C24 alkylpolyglycosides (e.g., C6-C20alkylpolyglycosides) having 1 to about 20 glycoside groups (e.g., about9 to about 20 glycoside groups); C6-C24 fatty acid ester ethoxylates,propoxylates or glycerides; and C4-C24 mono or dialkanolamides.

Specific alcohol alkoxylates include alcohol ethoxylate propoxylates,alcohol propoxylates, alcohol propoxylate ethoxylate propoxylates,alcohol ethoxylate butoxylates, and the like; nonylphenol ethoxylate,polyoxyethylene glycol ethers and the like; and polyalkylene oxide blockcopolymers including an ethylene oxide/propylene oxide block copolymersuch as those commercially available under the trademark PLURONIC(BASF-Wyandotte), and the like.

Suitable nonionic surfactants include low foaming nonionic surfactants.Examples of suitable low foaming nonionic surfactants include secondaryethoxylates, such as those sold under the trade name TERGITOL™, such asTERGITOL™ 15-S-7 (Union Carbide), Tergitol 15-S-3, Tergitol 15-S-9 andthe like. Other suitable classes of low foaming nonionic surfactantinclude alkyl or benzyl-capped polyoxyalkylene derivatives andpolyoxyethylene/polyoxypropylene copolymers.

A useful nonionic surfactant for use as a defoamer is nonylphenol havingan average of 12 moles of ethylene oxide condensed thereon, it being endcapped with a hydrophobic portion comprising an average of 30 moles ofpropylene oxide. Silicon-containing defoamers are also well-known andcan be employed in the compositions and methods of the presentinvention.

Suitable amphoteric surfactants include amine oxide compounds having theformula:

where R, R′, R″, and R′″ are each a C₁-C₂₄ alkyl, aryl or aralkyl groupthat can optionally contain one or more P, O, S or N heteroatoms.

Another class of suitable amphoteric surfactants includes betainecompounds having the formula:

where R, R′, R″ and R′″ are each a C₁-C₂₄ alkyl, aryl or aralkyl groupthat can optionally contain one or more P, O, S or N heteroatoms, and nis about 1 to about 10. Suitable surfactants include food gradesurfactants, linear alkylbenzene sulfonic acids and their salts, andethylene oxide/propylene oxide derivatives sold under the Pluronic™trade name. Suitable surfactants include those that are compatible as anindirect or direct food additive or substance; especially thosedescribed in the Code of Federal Regulations (CFR), Title 21-Food andDrugs, parts 170 to 186 (which is incorporated herein by reference).

Anionic surfactants suitable for the present cleaning compositions,include, for example, carboxylates such as alkylcarboxylates (carboxylicacid salts) and polyalkoxycarboxylates, alcohol ethoxylate carboxylates,nonylphenol ethoxylate carboxylates, and the like; sulfonates such asalkylsulfonates, alkylbenzenesulfonates, alkylarylsulfonates, sulfonatedfatty acid esters, and the like; sulfates such as sulfated alcohols,sulfated alcohol ethoxylates, sulfated alkylphenols, alkylsulfates,sulfosuccinates, alkylether sulfates, and the like; and phosphate esterssuch as alkylphosphate esters, and the like. Suitable anionics includesodium alkylarylsulfonate, alpha-olefin sulfonate, and fatty alcoholsulfates. Examples of suitable anionic surfactants include sodiumdodecylbenzene sulfonic acid, potassium laureth-7 sulfate, and sodiumtetradecenyl sulfonate.

The surfactant can be present at amounts listed in the tables or about0.01 to about 20 wt-% or about 0.1 to about 10 wt-%, about 0.2 to about5 wt-%.

pH Modifier

The pH modifier can be an organic or inorganic source of alkalinity or apH buffering agent. Nonlimiting examples include the alkali metalhydroxides, alkali metal carbonates, alkanolamines, salts of weakorganic acids, etc. Suitable pH modifiers include sodium hydroxide,lithium hydroxide, potassium hydroxide, sodium carbonate, lithiumcarbonate, potassium carbonate, the corresponding bicarbonate orsesquicarbonate salts, and mixtures thereof. Suitable pH modifiersinclude acetate, formate, and the like. Suitable pH modifiers have no oronly weak calcium sequestration capability at the pH of the usesolution.

The pH modifier can be present at amounts listed in the tables or about1 to about 70 wt-% or about 2 to about 50 wt-%, about 3 to about 30wt-%.

Processing Aid

Processing aids are materials which enhance the production process forthe detergent composition. They can serve as drying agents, modify therate of solidification, alter the transfer of water of hydration in theformula, or even act as the solidifying matrix itself. Processing aidscan have some overlap with other functionalities in the formula.Nonlimiting examples include silica, alkali metal silicates, urea,polyethylene glycols, solid surfactants, sodium carbonate, potassiumchloride, sodium sulfate, sodium hydroxide, water, etc. Which processingaid(s) is suitable would of course vary with the manufacturing procedureand specific detergent composition.

The processing aid can be present at amounts of about 1 to about 70wt-%, about 2 to about 50 wt-%, about 3 to about 30 wt-%.

Active Oxygen Compounds

The active oxygen compound acts to provide a source of active oxygen,but can also act to form at least a portion of the solidification agent.The active oxygen compound can be inorganic or organic, and can be amixture thereof. Some examples of active oxygen compound includeperoxygen compounds, and peroxygen compound adducts that are suitablefor use in forming the binding agent.

Many active oxygen compounds are peroxygen compounds. Any peroxygencompound generally known and that can function, for example, as part ofthe binding agent can be used. Examples of suitable peroxygen compoundsinclude inorganic and organic peroxygen compounds, or mixtures thereof.

The active oxygen compound can be in the present solid composition atamounts of about 1 to about 80 wt-%, about 5 to about 50 wt-%, or about10 wt-% to about 40 wt-%.

Inorganic Active Oxygen Compound

Examples of inorganic active oxygen compounds include the followingtypes of compounds or sources of these compounds, or alkali metal saltsincluding these types of compounds, or forming an adduct therewith:

hydrogen peroxide;

group 1 (IA) active oxygen compounds, for example lithium peroxide,sodium peroxide, and the like;

group 2 (IIA) active oxygen compounds, for example magnesium peroxide,calcium peroxide, strontium peroxide, barium peroxide, and the like;

group 12 (IIB) active oxygen compounds, for example zinc peroxide, andthe like;

group 13 (IIIA) active oxygen compounds, for example boron compounds,such as perborates, for example sodium perborate hexahydrate of theformula Na₂[Br₂(O₂)₂(OH)₄].6H₂O (also called sodium perboratetetrahydrate and formerly written as NaBO₃.4H₂O); sodium peroxyboratetetrahydrate of the formula Na₂Br₂(O₂)₂[(OH)₄].4H₂O (also called sodiumperborate trihydrate, and formerly written as NaBO₃.3H₂O); sodiumperoxyborate of the formula Na₂[B₂(O₂)₂(OH)₄] (also called sodiumperborate monohydrate and formerly written as NaBO₃.H₂O); and the like;e.g., perborate;

group 14 (IVA) active oxygen compounds, for example persilicates andperoxycarbonates, which are also called percarbonates, such aspersilicates or peroxycarbonates of alkali metals; and the like; e.g.,percarbonate, e.g., persilicate;

group 15 (VA) active oxygen compounds, for example peroxynitrous acidand its salts; peroxyphosphoric acids and their salts, for example,perphosphates; and the like; e.g., perphosphate;

group 16 (VIA) active oxygen compounds, for example peroxysulfuric acidsand their salts, such as peroxymonosulfuric and peroxydisulfuric acids,and their salts, such as persulfates, for example, sodium persulfate;and the like; e.g., persulfate;

group VIIa active oxygen compounds such as sodium periodate, potassiumperchlorate and the like.

Other active inorganic oxygen compounds can include transition metalperoxides; and other such peroxygen compounds, and mixtures thereof.

In certain embodiments, the compositions and methods of the presentinvention employ certain of the inorganic active oxygen compounds listedabove. Suitable inorganic active oxygen compounds include hydrogenperoxide, hydrogen peroxide adduct, group IIIA active oxygen compounds,group VIA active oxygen compound, group VA active oxygen compound, groupVIIA active oxygen compound, or mixtures thereof. Examples of suchinorganic active oxygen compounds include percarbonate, perborate,persulfate, perphosphate, persilicate, or mixtures thereof. Hydrogenperoxide presents an example of an inorganic active oxygen compound.Hydrogen peroxide can be formulated as a mixture of hydrogen peroxideand water, e.g., as liquid hydrogen peroxide in an aqueous solution. Themixture of solution can include about 5 to about 40 wt-% hydrogenperoxide or 5 to 50 wt-% hydrogen peroxide.

In an embodiment, the inorganic active oxygen compounds include hydrogenperoxide adduct. For example, the inorganic active oxygen compounds caninclude hydrogen peroxide, hydrogen peroxide adduct, or mixturesthereof. Any of a variety of hydrogen peroxide adducts are suitable foruse in the present compositions and methods. For example, suitablehydrogen peroxide adducts include percarbonate salt, urea peroxide,peracetyl borate, an adduct of H₂O₂ and polyvinyl pyrrolidone, sodiumpercarbonate, potassium percarbonate, mixtures thereof, or the like.Suitable hydrogen peroxide adducts include percarbonate salt, ureaperoxide, peracetyl borate, an adduct of H₂O₂ and polyvinyl pyrrolidone,or mixtures thereof. Suitable hydrogen peroxide adducts include sodiumpercarbonate, potassium percarbonate, or mixtures thereof, e.g., sodiumpercarbonate.

Organic Active Oxygen Compound

Any of a variety of organic active oxygen compounds can be employed inthe compositions and methods of the present invention. For example, theorganic s active oxygen compound can be a peroxycarboxylic acid, such asa mono- or di-peroxycarboxylic acid, an alkali metal salt includingthese types of compounds, or an adduct of such a compound. Suitableperoxycarboxylic acids include C₁-C₂₄ peroxycarboxylic acid, salt ofC₁-C₂₄ peroxycarboxylic acid, ester of C₁-C₂₄ peroxycarboxylic acid,diperoxycarboxylic acid, salt of diperoxycarboxylic acid, ester ofdiperoxycarboxylic acid, or mixtures thereof.

Suitable peroxycarboxylic acids include C₁-C₁₀ aliphaticperoxycarboxylic acid, salt of C₁-C₁₀ aliphatic peroxycarboxylic acid,ester of C₁-C₁₀ aliphatic peroxycarboxylic acid, or mixtures thereof,e.g., salt of or adduct of peroxyacetic acid; e.g., peroxyacetyl borate.Suitable diperoxycarboxylic acids include C₄-C₁₀ aliphaticdiperoxycarboxylic acid, salt of C₄-C₁₀ aliphatic diperoxycarboxylicacid, or ester of C₄-C₁₀ aliphatic diperoxycarboxylic acid, or mixturesthereof, e.g., a sodium salt of perglutaric acid, of persuccinic acid,of peradipic acid, or mixtures thereof.

Organic active oxygen compounds include other acids including an organicmoiety. Suitable organic active oxygen compounds include perphosphonicacids, perphosphonic acid salts, perphosphonic acid esters, or mixturesor combinations thereof.

Active Oxygen Compound Adducts

Active oxygen compound adducts include any generally known and that canfunction, for example, as a source of active oxygen and as part of thesolidified composition. Hydrogen peroxide adducts, or peroxyhydrates,are suitable. Some examples of source of alkalinity adducts include thefollowing: alkali metal percarbonates, for example sodium percarbonate(sodium carbonate peroxyhydrate), potassium percarbonate, rubidiumpercarbonate, cesium percarbonate, and the like; ammonium carbonateperoxyhydrate, and the like; urea peroxyhydrate, peroxyacetyl borate; anadduct of H₂O₂ polyvinyl pyrrolidone, and the like, and mixtures of anyof the above.

Antimicrobials

Antimicrobial agents are chemical compositions that can be used in asolid functional material that alone, or in combination with othercomponents, act to reduce or prevent microbial contamination anddeterioration of commercial products material systems, surfaces, etc. Insome aspects, these materials fall in specific classes includingphenolics, halogen compounds, quaternary ammonium compounds, metalderivatives, amines, alkanol amines, nitro derivatives, analides,organosulfur and sulfur-nitrogen compounds and miscellaneous compounds.

It should also be understood that the source of alkalinity used in theformation of compositions embodying the invention also act asantimicrobial agents, and can even provide sanitizing activity. In fact,in some embodiments, the ability of the source of alkalinity to act asan antimicrobial agent reduces the need for secondary antimicrobialagents within the composition. For example, percarbonate compositionshave been demonstrated to provide excellent antimicrobial action.Nonetheless, some embodiments incorporate additional antimicrobialagents.

The given antimicrobial agent, depending on chemical composition andconcentration, may simply limit further proliferation of numbers of themicrobe or may destroy all or a portion of the microbial population. Theterms “microbes” and “microorganisms” typically refer primarily tobacteria, virus, yeast, spores, and fungus microorganisms. In use, theantimicrobial agents are typically formed into a solid functionalmaterial that when diluted and dispensed, optionally, for example, usingan aqueous stream forms an aqueous disinfectant or sanitizer compositionthat can be contacted with a variety of surfaces resulting in preventionof growth or the killing of a portion of the microbial population. Athree log reduction of the microbial population results in a sanitizercomposition. The antimicrobial agent can be encapsulated, for example,to improve its stability.

Common antimicrobial agents include phenolic antimicrobials such aspentachlorophenol, orthophenylphenol, a chloro-p-benzylphenol,p-chloro-m-xylenol. Halogen containing antibacterial agents includesodium trichloroisocyanurate, sodium dichloro isocyanate (anhydrous ordihydrate), iodine-poly(vinylpyrrolidinone) complexes, bromine compoundssuch as 2-bromo-2-nitropropane-1,3-diol, and quaternary antimicrobialagents such as benzalkonium chloride, and didecyldimethyl ammoniumchloride. Other antimicrobial compositions such ashexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates suchas sodium dimethyldithiocarbamate, and a variety of other materials areknown in the art for their anti-microbial properties. In someembodiments, an antimicrobial component, such as TAED can be included inthe range of 0.001 to 75 wt-% of the composition, about 0.01 to 20 wt-%,or about 0.05 to about 10 wt-%.

If present in compositions, the additional antimicrobial agent can bethose listed in a table or about 0.01 to about 30 wt-% of thecomposition, 0.05 to about 10 wt-%, or about 0.1 to about 5 wt-%. In ause solution the additional antimicrobial agent can be about 0.001 toabout 5 wt-% of the composition, about 0.01 to about 2 wt-%, or about0.05 to about 0.5 wt-

Activators

In some embodiments, the antimicrobial activity or bleaching activity ofthe composition can be enhanced by the addition of a material which,when the composition is placed in use, reacts with the active oxygen toform an activated component. For example, in some embodiments, a peracidor a peracid salt is formed. For example, in some embodiments,tetraacetylethylene diamine can be included within the composition toreact with the active oxygen and form a peracid or a peracid salt thatacts as an antimicrobial agent. Other examples of active oxygenactivators include transition metals and their compounds, compounds thatcontain a carboxylic, nitrile, or ester moiety, or other such compoundsknown in the art. In an embodiment, the activator includestetraacetylethylene diamine; transition metal; compound that includescarboxylic, nitrile, amine, or ester moiety; or mixtures thereof.

In some embodiments, an activator component can include in the range of0.001 to 75 wt-%, about 0.01 to about 20 wt-%, or about 0.05 to about 10wt-% of the composition.

In an embodiment, the activator for the source of alkalinity combineswith the active oxygen to form an antimicrobial agent.

The solid composition typically remains stable even in the presence ofactivator of the source of alkalinity. In many compositions it would beexpected to react with and destabilize or change the form of the sourceof alkalinity. In contrast, in an embodiment of the present invention,the composition remains solid; it does not swell, crack, or enlarge asit would if the source of alkalinity were reacting with the activator.

In an embodiment, the composition includes a solid block, and anactivator material for the active oxygen is coupled to the solid block.The activator can be coupled to the solid block by any of a variety ofmethods for coupling one solid cleaning composition to another. Forexample, the activator can be in the form of a solid that is bound,affixed, glued or otherwise adhered to the solid block. Alternatively,the solid activator can be formed around and encasing the block. By wayof further example, the solid activator can be coupled to the solidblock by the container or package for the cleaning composition, such asby a plastic or shrink wrap or film.

Additional Bleaching Agents

Additional bleaching agents for use in inventive formulations forlightening or whitening a substrate, include bleaching compounds capableof liberating an active halogen species, such as Cl₂, Br₂, 12, ClO₂,BrO₂, IO₂, —OCl⁻, —OBr⁻ and/or, —OI⁻, under conditions typicallyencountered during the cleansing process. Suitable bleaching agents foruse in the present cleaning compositions include, for example,chlorine-containing compounds such as a chlorite, a hypochlorite,chloramine. Suitable halogen-releasing compounds include the alkalimetal dichloroisocyanurates, chlorinated trisodium phosphate, the alkalimetal hypochlorites, alkali metal chlorites, monochloramine anddichloramine, and the like, and mixtures thereof. Encapsulated chlorinesources may also be used to enhance the stability of the chlorine sourcein the composition (see, for example, U.S. Pat. Nos. 4,618,914 and4,830,773, the disclosure of which is incorporated by reference herein).A bleaching agent may also be an additional peroxygen or active oxygensource such as hydrogen peroxide, perborates, for example sodiumperborate mono and tetrahydrate, sodium carbonate peroxyhydrate,phosphate peroxyhydrates, and potassium permonosulfate, with and withoutactivators such as tetraacetylethylene diamine, and the like, asdiscussed above.

A cleaning composition may include a minor but effective additionalamount of a bleaching agent above that already available from thestabilized source of alkalinity, e.g., about 0.1-10 wt-% or about 1-6wt-%. The present solid compositions can include bleaching agent in anamount those listed in a table or about 0.1 to about 60 wt-%, about 1 toabout 20 wt-%, about 3 to about 8 wt-%, or about 3 to about 6 wt-%.

Hardening Agents

The detergent compositions may also include a hardening agent inaddition to, or in the form of, the builder. A hardening agent is acompound or system of compounds, organic or inorganic, whichsignificantly contributes to the uniform solidification of thecomposition. The hardening agents should be compatible with the cleaningagent and other active ingredients of the composition and should becapable of providing an effective amount of hardness and/or aqueoussolubility to the processed detergent composition. The hardening agentsshould also be capable of forming a homogeneous matrix with the cleaningagent and other ingredients when mixed and solidified to provide auniform dissolution of the cleaning agent from the detergent compositionduring use.

The amount of hardening agent included in the detergent composition willvary according to factors including, but not limited to: the type ofdetergent composition being prepared, the ingredients of the detergentcomposition, the intended use of the detergent composition, the quantityof dispensing solution applied to the detergent composition over timeduring use, the temperature of the dispensing solution, the hardness ofthe dispensing solution, the physical size of the detergent composition,the concentration of the other ingredients, and the concentration of thecleaning agent in the composition. The amount of the hardening agentincluded in the solid detergent composition should be effective tocombine with the cleaning agent and other ingredients of the compositionto form a homogeneous mixture under continuous mixing conditions and atemperature at or below the melting temperature of the hardening agent.

The hardening agent may also form a matrix with the cleaning agent andother ingredients which will harden to a solid form under ambienttemperatures of about 30° C. to about 50° C., particularly about 35° C.to about 45° C., after mixing ceases and the mixture is dispensed fromthe mixing system, within about 1 minute to about 3 hours, particularlyabout 2 minutes to about 2 hours, and particularly about 5 minutes toabout 1 hour. A minimal amount of heat from an external source may beapplied to the mixture to facilitate processing of the mixture. Theamount of the hardening agent included in the detergent compositionshould be effective to provide a desired hardness and desired rate ofcontrolled solubility of the processed composition when placed in anaqueous medium to achieve a desired rate of dispensing the cleaningagent from the solidified composition during use.

The hardening agent may be an organic or an inorganic hardening agent. Aparticular organic hardening agent is a polyethylene glycol (PEG)compound. The solidification rate of detergent compositions comprising apolyethylene glycol hardening agent will vary, at least in part,according to the amount and the molecular weight of the polyethyleneglycol added to the composition. Examples of suitable polyethyleneglycols include, but are not limited to: solid polyethylene glycols ofthe general formula H(OCH₂CH₂)_(n)OH, where n is greater than 15, moreparticularly about 30 to about 1700. Typically, the polyethylene glycolis a solid in the form of a free-flowing powder or flakes, having amolecular weight of about 1,000 to about 100,000, particularly having amolecular weight of at least about 1,450 to about 20,000, moreparticularly between about 1,450 to about 8,000. The polyethylene glycolis present at a concentration of from about 1% to about 75% by weightand particularly about 3% to about 15% by weight. Suitable polyethyleneglycol compounds include, but are not limited to: PEG 4000, PEG 1450,and PEG 8000 among others, with PEG 4000 and PEG 8000 being mostpreferred. An example of a commercially available solid polyethyleneglycol includes, but is not limited to: CARBOWAX, available from UnionCarbide Corporation, Houston, Tex.

Particular inorganic hardening agents are hydratable inorganic salts,including, but not limited to: sulfates, acetates, and bicarbonates. Inan exemplary embodiment, the inorganic hardening agents are present atconcentrations of up to about 50% by weight, particularly about 5% toabout 25% by weight, and more particularly about 5% to about 15% byweight.

Urea particles may also be employed as hardeners in the detergentcompositions. The solidification rate of the compositions will vary, atleast in part, to factors including, but not limited to: the amount, theparticle size, and the shape of the urea added to the detergentcomposition. For example, a particulate form of urea may be combinedwith a cleaning agent and other ingredients, as well as a minor buteffective amount of water. The amount and particle size of the urea iseffective to combine with the cleaning agent and other ingredients toform a homogeneous mixture without the application of heat from anexternal source to melt the urea and other ingredients to a moltenstage. The amount of urea included in the solid detergent compositionshould be effective to provide a desired hardness and desired rate ofsolubility of the composition when placed in an aqueous medium toachieve a desired rate of dispensing the cleaning agent from thesolidified composition during use. In an exemplary embodiment, thedetergent composition includes between about 5% to about 90% by weighturea, particularly between about 8% and about 40% by weight urea, andmore particularly between about 10% and about 30% by weight urea.

The urea may be in the form of prilled beads or powder. Prilled urea isgenerally available from commercial sources as a mixture of particlesizes ranging from about 8-15 U.S. mesh, as for example, from ArcadianSohio Company, Nitrogen Chemicals Division. A prilled form of urea ismilled to reduce the particle size to about 50 U.S. mesh to about 125U.S. mesh, particularly about 75-100 U.S. mesh, particularly using a wetmill such as a single or twin-screw extruder, a Teledyne mixer, a Rossemulsifier, and the like.

Secondary Hardening Agents/Solubility Modifiers.

The present compositions may include a minor but effective amount of asecondary hardening agent, as for example, an amide such stearicmonoethanolamide or lauric diethanolamide, or an alkylamide, and thelike; a solid polyethylene glycol, or a solid EO/PO block copolymer, andthe like; starches that have been made water-soluble through an acid oralkaline treatment process; various inorganics that impart solidifyingproperties to a heated composition upon cooling, and the like. Suchcompounds may also vary the solubility of the composition in an aqueousmedium during use such that the cleaning agent and/or other activeingredients may be dispensed from the solid composition over an extendedperiod of time. The composition may include a secondary hardening agentin an amount those listed in a table or about 5 to about 20 wt-% orabout 10 to about 15 wt-%.

Detergent Fillers

A cleaning composition may include an effective amount of one or more ofa detergent filler which does not perform as a cleaning agent per se,but cooperates with the cleaning agent to enhance the overallprocessability of the composition. Examples of fillers suitable for usein the present cleaning compositions include sodium sulfate, sodiumchloride, starch, sugars, C₁-C₁₀ alkylene glycols such as propyleneglycol, and the like. A filler such as a sugar (e.g. sucrose) can aiddissolution of a solid composition by acting as a disintegrant. Adetergent filler can be included in an amount listed in a table or up toabout 50 wt-%, of about 1 to about 20 wt-%, about 3 to about 15 wt-%,about 1 to about 30 wt-%, or about 1.5 to about 25 wt-%.

Defoaming Agents

An effective amount of a defoaming agent for reducing the stability offoam may also be included in the present cleaning compositions. Thecleaning composition can include about 0.0001-5 wt-% of a defoamingagent, e.g., about 0.01-3 wt-%. The defoaming agent can be provided inan amount of about 0.0001% to about 10 wt-%, about 0.001% to about 5wt-%, or about 0.01% to about 1.0 wt-%.

Examples of defoaming agents suitable for use in the presentcompositions include silicone compounds such as silica dispersed inpolydimethylsiloxane, EO/PO block copolymers, alcohol alkoxylates, fattyamides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols,fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters,alkyl phosphate esters such as monostearyl phosphate, and the like. Adiscussion of defoaming agents may be found, for example, in U.S. Pat.No. 3,048,548 to Martin et al., U.S. Pat. No. 3,334,147 to Brunelle etal., and U.S. Pat. No. 3,442,242 to Rue et al., the disclosures of whichare incorporated by reference herein.

Anti-Redeposition Agents

A cleaning composition may also include an anti-redeposition agentcapable of facilitating sustained suspension of soils in a cleaningsolution and preventing the removed soils from being redeposited ontothe substrate being cleaned. Examples of suitable anti-redepositionagents include fatty acid amides, fluorocarbon surfactants, complexphosphate esters, styrene maleic anhydride copolymers, and cellulosicderivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, andthe like. A cleaning composition may include about 0.5 to about 10 wt-%,e.g., about 1 to about 5 wt-%, of an anti-redeposition agent.

Optical Brighteners

Optical brightener is also referred to as fluorescent whitening agentsor fluorescent brightening agents provide optical compensation for theyellow cast in fabric substrates. With optical brighteners yellowing isreplaced by light emitted from optical brighteners present in the areacommensurate in scope with yellow color. The violet to blue lightsupplied by the optical brighteners combines with other light reflectedfrom the location to provide a substantially complete or enhanced brightwhite appearance. This additional light is produced by the brightenerthrough fluorescence. Optical brighteners absorb light in theultraviolet range 275 through 400 nm. and emit light in the ultravioletblue spectrum 400-500 nm.

Fluorescent compounds belonging to the optical brightener family aretypically aromatic or aromatic heterocyclic materials often containingcondensed ring system. An important feature of these compounds is thepresence of an uninterrupted chain of conjugated double bonds associatedwith an aromatic ring. The number of such conjugated double bonds isdependent on substituents as well as the planarity of the fluorescentpart of the molecule. Most brightener compounds are derivatives ofstilbene or 4,4′-diamino stilbene, biphenyl, five membered heterocycles(triazoles, oxazoles, imidazoles, etc.) or six membered heterocycles(cumarins, naphthalamides, triazines, etc.). The choice of opticalbrighteners for use in detergent compositions will depend upon a numberof factors, such as the type of detergent, the nature of othercomponents present in the detergent composition, the temperature of thewash water, the degree of agitation, and the ratio of the materialwashed to the tub size. The brightener selection is also dependent uponthe type of material to be cleaned, e.g., cottons, synthetics, etc.Since most laundry detergent products are used to clean a variety offabrics, the detergent compositions should contain a mixture ofbrighteners which are effective for a variety of fabrics. It is ofcourse necessary that the individual components of such a brightenermixture be compatible.

Optical brighteners useful in the present invention are commerciallyavailable and will be appreciated by those skilled in the art.Commercial optical brighteners which may be useful in the presentinvention can be classified into subgroups, which include, but are notnecessarily limited to, derivatives of stilbene, pyrazoline, coumarin,carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles,5- and 6-membered-ring heterocycles and other miscellaneous agents.Examples of these types of brighteners are disclosed in “The Productionand Application of Fluorescent Brightening Agents”, M. Zahradnik,Published by John Wiley & Sons, New York (1982), the disclosure of whichis incorporated herein by reference.

Stilbene derivatives which may be useful in the present inventioninclude, but are not necessarily limited to, derivatives ofbis(triazinyl)amino-stilbene; bisacylamino derivatives of stilbene;triazole derivatives of stilbene; oxadiazole derivatives of stilbene;oxazole derivatives of stilbene; and styryl derivatives of stilbene.

For laundry cleaning or sanitizing compositions, suitable opticalbrighteners include stilbene derivatives, which can be employed atconcentrations of up to 1 wt-%.

Stabilizing Agents

The solid detergent composition may also include a stabilizing agent.Examples of suitable stabilizing agents include, but are not limited to:borate, calcium/magnesium ions, propylene glycol, and mixtures thereof.The composition need not include a stabilizing agent, but when thecomposition includes a stabilizing agent, it can be included in anamount that provides the desired level of stability of the composition.Suitable ranges of the stabilizing agent include those listed in a tableor up to about 20 wt-%, about 0.5 to about 15 wt-%, or about 2 to about10 wt-%.

Dispersants

The solid detergent composition may also include a dispersant. Examplesof suitable dispersants that can be used in the solid detergentcomposition include, but are not limited to: maleic acid/olefincopolymers, polyacrylic acid, and mixtures thereof. The composition neednot include a dispersant, but when a dispersant is included it can beincluded in an amount that provides the desired dispersant properties.Suitable ranges of the dispersant in the composition can be those listedin a table or up to about 20 wt-%, about 0.5 to about 15 wt-%, or about2 to about 9 wt-%.

Enzymes

Enzymes that can be included in the solid detergent composition includethose enzymes that aid in the removal of starch and/or protein stains.Suitable types of enzymes include, but are not limited to: proteases,alpha-amylases, and mixtures thereof. Suitable proteases that can beused include, but are not limited to: those derived from Bacilluslicheniformix, Bacillus lenus, Bacillus alcalophilus, and Bacillusamyloliquefacins. Suitable alpha-amylases include Bacillus subtilis,Bacillus amyloliquefaciens, and Bacillus licheniformis. The compositionneed not include an enzyme, but when the composition includes an enzyme,it can be included in an amount that provides the desired enzymaticactivity when the solid detergent composition is provided as a usecomposition. Suitable ranges of the enzyme in the composition includethose listed in a table or up to about 15 wt-%, about 0.5 to about 10wt-%, or about 1 to about 5 wt-%.

Thickeners

The solid detergent compositions can include a rheology modifier or athickener. The rheology modifier may provide the following functions:increasing the viscosity of the compositions; increasing the particlesize of liquid use solutions when dispensed through a spray nozzle;providing the use solutions with vertical cling to surfaces; providingparticle suspension within the use solutions; or reducing theevaporation rate of the use solutions.

The rheology modifier may provide a use composition that is pseudoplastic, in other words the use composition or material when leftundisturbed (in a shear mode), retains a high viscosity. However, whensheared, the viscosity of the material is substantially but reversiblyreduced. After the shear action is removed, the viscosity returns. Theseproperties permit the application of the material through a spray head.When sprayed through a nozzle, the material undergoes shear as it isdrawn up a feed tube into a spray head under the influence of pressureand is sheared by the action of a pump in a pump action sprayer. Ineither case, the viscosity can drop to a point such that substantialquantities of the material can be applied using the spray devices usedto apply the material to a soiled surface. However, once the materialcomes to rest on a soiled surface, the materials can regain highviscosity to ensure that the material remains in place on the soil. Inan embodiment, the material can be applied to a surface resulting in asubstantial coating of the material that provides the cleaningcomponents in sufficient concentration to result in lifting and removalof the hardened or baked-on soil. While in contact with the soil onvertical or inclined surfaces, the thickeners in conjunction with theother components of the cleaner minimize dripping, sagging, slumping orother movement of the material under the effects of gravity. Thematerial should be formulated such that the viscosity of the material isadequate to maintain contact substantial quantities of the film of thematerial with the soil for at least a minute, five minutes or more.

Examples of suitable thickeners or rheology modifiers are polymericthickeners including, but not limited to: polymers or natural polymersor gums derived from plant or animal sources. Such materials may bepolysaccharides such as large polysaccharide molecules havingsubstantial thickening capacity. Thickeners or rheology modifiers alsoinclude clays.

A substantially soluble polymeric thickener can be used to provideincreased viscosity or increased conductivity to the use compositions.Examples of polymeric thickeners for the aqueous compositions of theinvention include, but are not limited to: carboxylated vinyl polymerssuch as polyacrylic acids and sodium salts thereof, ethoxylatedcellulose, polyacrylamide thickeners, cross-linked, xanthancompositions, sodium alginate and algin products, hydroxypropylcellulose, hydroxyethyl cellulose, and other similar aqueous thickenersthat have some substantial proportion of water solubility. Examples ofsuitable commercially available thickeners include, but are not limitedto: Acusol, available from Rohm & Haas Company, Philadelphia, Pa.; andCarbopol, available from B.F. Goodrich, Charlotte, N.C.

Examples of suitable polymeric thickeners include, but not limited to:polysaccharides. An example of a suitable commercially availablepolysaccharide includes, but is not limited to, Diutan, available fromKelco Division of Merck, San Diego, Calif. Thickeners for use in thesolid detergent compositions further include polyvinyl alcoholthickeners, such as, fully hydrolyzed (greater than 98.5 mol acetatereplaced with the —OH function).

An example of a suitable polysaccharide includes, but is not limited to,xanthans. Such xanthan polymers are suitable due to their high watersolubility, and great thickening power. Xanthan is an extracellularpolysaccharide of Xanthomonas campestras. Xanthan may be made byfermentation based on corn sugar or other corn sweetener by-products.Xanthan includes a poly beta-(1-4)-D-Glucopyranosyl backbone chain,similar to that found in cellulose. Aqueous dispersions of xanthan gumand its derivatives exhibit novel and remarkable rheological properties.Low concentrations of the gum have relatively high viscosities whichpermit it to be used economically. Xanthan gum solutions exhibit highpseudo plasticity, i.e. over a wide range of concentrations, rapid shearthinning occurs that is generally understood to be instantaneouslyreversible. Non-sheared materials have viscosities that appear to beindependent of the pH and independent of temperature over wide ranges.Suitable xanthan materials include crosslinked xanthan materials.Xanthan polymers can be crosslinked with a variety of known covalentreacting crosslinking agents reactive with the hydroxyl functionality oflarge polysaccharide molecules and can also be crosslinked usingdivalent, trivalent or polyvalent metal ions. Such crosslinked xanthangels are disclosed in U.S. Pat. No. 4,782,901, which is hereinincorporated by reference. Suitable crosslinking agents for xanthanmaterials include, but are not limited to: metal cations such as Al+3,Fe+3, Sb+3, Zr+4 and other transition metals. Examples of suitablecommercially available xanthans include, but are not limited to:KELTROL®, KELZAN® AR, KELZAN® D35, KELZAN® S, KELZAN® XZ, available fromKelco Division of Merck, San Diego, Calif. Known organic crosslinkingagents can also be used. A suitable crosslinked xanthan is KELZAN® AR,which provides a pseudo plastic use solution that can produce largeparticle size mist or aerosol when sprayed.

The thickener can be in the present composition at amounts listed in atable or about 0.05 to about 10 wt-%, about 0.1 to about 8 wt-%, orabout 0.2 wt-% to about 6 wt-%.

Dyes/Odorants

Various dyes, odorants including perfumes, and other aesthetic enhancingagents may also be included in the composition. Dyes may be included toalter the appearance of the composition, as for example, Direct Blue 86(Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (AmericanCyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow17 (Sigma Chemical), Sap Green (Keyston Analine and Chemical), MetanilYellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis),Sandolan Blue/Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color andChemical), Fluorescein (Capitol Color and Chemical), Acid Green 25(Ciba-Geigy), and the like.

Fragrances or perfumes that may be included in the compositions include,for example, terpenoids such as citronellol, aldehydes such as amylcinnamaldehyde, a jasmine such as C1S-jasmine or jasmal, vanillin, andthe like.

The dye or odorant can be in the present solid composition at amounts ofabout 0.005 to about 5 wt-%, about 0.01 to about 3 wt-%, or about 0.2wt-% to about 3 wt-%.

Use Compositions

The present calcium magnesium gluconate composition or a compositioncontaining the calcium magnesium gluconate composition can be providedin the form of a concentrate or a use solution. In general, aconcentrate refers to a composition that is intended to be diluted withwater to provide a use solution that contacts an object to provide thedesired cleaning, rising, or the like. A use solution may be preparedfrom the concentrate by diluting the concentrate with water at adilution ratio that provides a use solution having desired detersiveproperties. In an exemplary embodiment, the concentrate may be dilutedat a weight ratio of diluent to concentrate of at least about 1:1 orabout 1:1 to about 2000:1.

The concentrate may be diluted with water at the location of use toprovide the use solution. When the detergent composition is used in anautomatic warewashing or dishwashing machine, it is expected that thatthe location of use will be inside the automatic warewashing machine.For example, when the detergent composition is used in a residentialwarewashing machine, the composition may be placed in the detergentcompartment of the warewashing machine. Depending on the machine, thedetergent may be provided in a unit dose form or in a multi-use form. Inlarger warewashing machines, a large quantity of detergent compositionmay be provided in a compartment that allows for the release of a singledose amount of the detergent composition for each wash cycle. Such acompartment may be provided as part of the warewashing machine or as aseparate structure connected to the warewashing machine. For example, ablock of the detergent composition may be provided in a hopper andintroduced into the warewashing machine when water is sprayed againstthe surface of the block to provide a liquid concentrate.

The detergent composition may also be dispensed from a spray-typedispenser. Briefly, a spray-type dispenser functions by impinging awater spray upon an exposed surface of the detergent composition todissolve a portion of the detergent composition, and then immediatelydirecting the use solution out of the dispenser to a storage reservoiror directly to a point of use. When used, the product may be removedfrom the packaging (e.g. film) and inserted into the dispenser. Thespray of water may be made by a nozzle in a shape that conforms to theshape of the solid detergent composition. The dispenser enclosure mayalso closely fit the shape of the detergent composition to preventintroducing and dispensing an incorrect detergent composition.

Embodiments of Solids

The present invention also relates to solid cleaning compositionsincluding the calcium magnesium gluconate composition. For example, thepresent invention includes a cast solid block of the calcium magnesiumgluconate composition and other components as desired. By way of furtherexample, the present invention includes a pressed solid block or puckincluding calcium magnesium gluconate composition.

According to the present invention, a solid cleaning composition of acalcium magnesium gluconate composition can be prepared by a methodincluding: providing a powder or crystalline form of calcium magnesiumgluconate composition; melting the powder or crystalline form of thecalcium magnesium gluconate composition; transferring the molten calciummagnesium gluconate composition into a mold; and cooling the moltencomposition to solidify it.

According to the present invention, a solid cleaning composition of acalcium magnesium gluconate composition can be prepared by a methodincluding: providing a powder or crystalline form of a calcium magnesiumgluconate composition; gently pressing the calcium magnesium gluconateto form a solid (e.g., block or puck).

A solid cleaning or rinsing composition as used in the presentdisclosure encompasses a variety of forms including, for example,solids, pellets, blocks, and tablets, but not powders. It should beunderstood that the term “solid” refers to the state of the detergentcomposition under the expected conditions of storage and use of thesolid cleaning composition. In general, it is expected that thedetergent composition will remain a solid when provided at a temperatureof up to about 100° F. or greater than 120° F.

In certain embodiments, the solid cleaning composition is provided inthe form of a unit dose. A unit dose refers to a solid cleaningcomposition unit sized so that the entire unit is used during a singlewashing cycle. When the solid cleaning composition is provided as a unitdose, it can have a mass of about 1 g to about 50 g. In otherembodiments, the composition can be a solid, a pellet, or a tablethaving a size of about 50 g to 250 g, of about 100 g or greater, orabout 40 g to about 11,000 g.

In other embodiments, the solid cleaning composition is provided in theform of a multiple-use solid, such as, a block or a plurality ofpellets, and can be repeatedly used to generate aqueous detergentcompositions for multiple washing cycles. In certain embodiments, thesolid cleaning composition is provided as a solid having a mass of about5 g to 10 kg. In certain embodiments, a multiple-use form of the solidcleaning composition has a mass of about 1 to 10 kg. In furtherembodiments, a multiple-use form of the solid cleaning composition has amass of about 5 kg to about 8 kg. In other embodiments, a multiple-useform of the solid cleaning composition has a mass of about 5 g to about1 kg, or about 5 g and to 500 g.

Packaging System

In some embodiments, the solid composition can be packaged. Thepackaging receptacle or container may be rigid or flexible, and composedof any material suitable for containing the compositions producedaccording to the invention, as for example glass, metal, plastic film orsheet, cardboard, cardboard composites, paper, and the like.

Advantageously, since the composition is processed at or near ambienttemperatures, the temperature of the processed mixture is low enough sothat the mixture may be formed directly in the container or otherpackaging system without structurally damaging the material. As aresult, a wider variety of materials may be used to manufacture thecontainer than those used for compositions that processed and dispensedunder molten conditions.

Suitable packaging used to contain the compositions is manufactured froma flexible, easy opening film material.

Dispensing of the Processed Compositions

The solid cleaning composition according to the present invention can bedispensed in any suitable method generally known. The cleaning orrinsing composition can be dispensed from a spray-type dispenser such asthat disclosed in U.S. Pat. Nos. 4,826,661, 4,690,305, 4,687,121,4,426,362 and in U.S. Pat. Nos. Re 32,763 and 32,818, the disclosures ofwhich are incorporated by reference herein. Briefly, a spray-typedispenser functions by impinging a water spray upon an exposed surfaceof the solid composition to dissolve a portion of the composition, andthen immediately directing the concentrate solution including thecomposition out of the dispenser to a storage reservoir or directly to apoint of use. When used, the product is removed from the package (e.g.)film and is inserted into the dispenser. The spray of water can be madeby a nozzle in a shape that conforms to the solid shape. The dispenserenclosure can also closely fit the detergent shape in a dispensingsystem that prevents the introduction and dispensing of an incorrectdetergent. The aqueous concentrate is generally directed to a use locus.

In an embodiment, the present composition can be dispensed by immersingeither intermittently or continuously in water. The composition can thendissolve, for example, at a controlled or predetermined rate. The ratecan be effective to maintain a concentration of dissolved cleaning agentthat is effective for cleaning.

In an embodiment, the present composition can be dispensed by scrapingsolid from the solid composition and contacting the scrapings withwater. The scrapings can be added to water to provide a concentration ofdissolved cleaning agent that is effective for cleaning.

Methods Employing the Present Compositions

In an embodiment, the present invention includes methods employing thepresent calcium magnesium gluconate composition or a compositionincluding the calcium magnesium gluconate composition. For example, inan embodiment, the present invention includes a method of reducingcorrosion of a surface of a material exposed to alkalinity. The methodincludes contacting the surface with a liquid containing the calciummagnesium gluconate composition or a composition including the calciummagnesium gluconate composition. The liquid can include dissolved ordispersed composition. The method can also include providing the calciummagnesium gluconate composition or a composition including thegluconate; and dissolving the composition in a liquid diluent (e.g.,water). The method can apply the liquid to any of a variety of surfacesor objects including surfaces or objects including or made of glass,ceramic, porcelain, or aluminum.

The present composition may be applied in any situation where it isdesired to prevent surface corrosion or etching. The present compositionmay be employed in a commercial warewashing detergent composition toprotect articles from corrosion or etching in automatic dishwashing orwarewashing machines during cleaning, in the cleaning of transportationvehicles, or in the cleaning of bottles. Applications in which thepresent composition may be used include: warewashing, rinse aids,vehicle cleaning and care applications, hard surface cleaning anddestaining, kitchen and bath cleaning and destaining, cleaning-in-placeoperations in food and beverage production facilities, food processingequipment, general purpose cleaning and destaining, bottlewashing, andindustrial or household cleaners.

Clean in Place

Other hard surface cleaning applications for the corrosion inhibitorcompositions of the invention (or cleaning compositions including them)include clean-in-place systems (CIP), clean-out-of-place systems (COP),washer-decontaminators, sterilizers, textile laundry machines, ultra andnano-filtration systems and indoor air filters. COP systems can includereadily accessible systems including wash tanks, soaking vessels, mopbuckets, holding tanks, scrub sinks, vehicle parts washers,non-continuous batch washers and systems, and the like.

The cleaning of the in-place system or other surface (i.e., removal ofunwanted offal therein) can be accomplished with a formulated detergentincluding the corrosion inhibitor compositions of the invention which isintroduced with heated water. CIP typically employ flow rates on theorder of about 40 to about 600 liters per minute, temperatures fromambient up to about 70° C., and contact times of at least about 10seconds, for example, about 30 to about 120 seconds.

A method of cleaning substantially fixed in-place process facilitiesincludes the following steps. The use solution of the invention isintroduced into the process facilities at a temperature in the range ofabout 4° C. to 60° C. After introduction of the use solution, thesolution is held in a container or circulated throughout the system fora time sufficient to clean the process facilities (i.e., to removeundesirable soil). After the surfaces have been cleaned by means of thepresent composition, the use solution is drained. Upon completion of thecleaning step, the system optionally may be rinsed with other materialssuch as potable water. The composition can be circulated through theprocess facilities for 10 minutes or less.

Embodiments of Ratios

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2 and the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2 and the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater. In an embodiment, theweight ratio of water soluble calcium salt to water soluble magnesiumsalt is 1-2:1-2 and the weight ratio of water soluble magnesium salt togluconate is 1.5:1 or greater. In an embodiment, the weight ratio ofwater soluble calcium salt to water soluble magnesium salt is 1-2:1-2and the weight ratio of water soluble magnesium salt to gluconate is 2:1or greater.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50 and the weight ratio ofwater soluble magnesium salt to gluconate is 1:1 or greater. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50 and the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50 and the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50 and the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25 and the weight ratio ofwater soluble magnesium salt to gluconate is 1:1 or greater. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25 and the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25 and the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25 and the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1 and the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1:1 and the weight ratio of water soluble magnesiumsalt to gluconate is 1.25:1 or greater. In an embodiment, the weightratio of water soluble calcium salt to water soluble magnesium salt is1:1 and the weight ratio of water soluble magnesium salt to gluconate is1.5:1 or greater. In an embodiment, the weight ratio of water solublecalcium salt to water soluble magnesium salt is 1:1 and the weight ratioof water soluble magnesium salt to gluconate is 2:1 or greater.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2 and the weight ratio of watersoluble calcium salt to gluconate is 1-19:1-13. In an embodiment, theweight ratio of water soluble calcium salt to water soluble magnesiumsalt is 1-2:1-2 and the weight ratio of water soluble calcium salt togluconate is 1-15:1-8. In an embodiment, the weight ratio of watersoluble calcium salt to water soluble magnesium salt is 1-2:1-2 and theweight ratio of water soluble calcium salt to gluconate is 3-10:1-5. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2 and the weight ratio of water solublecalcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50 and the weight ratio ofwater soluble calcium salt to gluconate is 1-19:1-13. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-1.50:1-1.50 and the weight ratio of water solublecalcium salt to gluconate is 1-15:1-8. In an embodiment, the weightratio of water soluble calcium salt to water soluble magnesium salt is1-1.50:1-1.50 and the weight ratio of water soluble calcium salt togluconate is 3-10:1-5. In an embodiment, the weight ratio of watersoluble calcium salt to water soluble magnesium salt is 1-1.50:1-1.50and the weight ratio of water soluble calcium salt to gluconate is3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25 and the weight ratio ofwater soluble calcium salt to gluconate is 1-19:1-13. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-1.25:1-1.25 and the weight ratio of water solublecalcium salt to gluconate is 1-15:1-8. In an embodiment, the weightratio of water soluble calcium salt to water soluble magnesium salt is1-1.25:1-1.25 and the weight ratio of water soluble calcium salt togluconate is 3-10:1-5. In an embodiment, the weight ratio of watersoluble calcium salt to water soluble magnesium salt is 1-1.25:1-1.25and the weight ratio of water soluble calcium salt to gluconate is3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1 and the weight ratio of watersoluble calcium salt to gluconate is 1-19:1-13. In an embodiment, theweight ratio of water soluble calcium salt to water soluble magnesiumsalt is 1:1 and the weight ratio of water soluble calcium salt togluconate is 1-15:1-8. In an embodiment, the weight ratio of watersoluble calcium salt to water soluble magnesium salt is 1:1 and theweight ratio of water soluble calcium salt to gluconate is 3-10:1-5. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1:1 and the weight ratio of water solublecalcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 1:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 1-19:1-13. In an embodiment, the weightratio of water soluble magnesium salt to gluconate is 1:1 or greater andthe weight ratio of water soluble calcium salt to gluconate is 1-15:1-8.In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 1:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 3-10:1-5. In an embodiment, the weightratio of water soluble magnesium salt to gluconate is 1:1 or greater andthe weight ratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 1.25:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 1-19:1-13. In an embodiment, the weightratio of water soluble magnesium salt to gluconate is 1.25:1 or greaterand the weight ratio of water soluble calcium salt to gluconate is1-15:1-8. In an embodiment, the weight ratio of water soluble magnesiumsalt to gluconate is 1.25:1 or greater and the weight ratio of watersoluble calcium salt to gluconate is 3-10:1-5. In an embodiment, theweight ratio of water soluble magnesium salt to gluconate is 1.25:1 orgreater and the weight ratio of water soluble calcium salt to gluconateis 3-8:2-4.

In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 1.5:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 1-19:1-13. In an embodiment, the weightratio of water soluble magnesium salt to gluconate is 1.5:1 or greaterand the weight ratio of water soluble calcium salt to gluconate is1-15:1-8. In an embodiment, the weight ratio of water soluble magnesiumsalt to gluconate is 1.5:1 or greater and the weight ratio of watersoluble calcium salt to gluconate is 3-10:1-5. In an embodiment, theweight ratio of water soluble magnesium salt to gluconate is 1.5:1 orgreater and the weight ratio of water soluble calcium salt to gluconateis 3-8:2-4.

In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 2:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 1-19:1-13. In an embodiment, the weightratio of water soluble magnesium salt to gluconate is 2:1 or greater andthe weight ratio of water soluble calcium salt to gluconate is 1-15:1-8.

In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 2:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 3-10:1-5. In an embodiment, the weightratio of water soluble magnesium salt to gluconate is 2:1 or greater andthe weight ratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 1:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 1-15:1-8. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 1:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 3-10:1-5. In an embodiment, theweight ratio of water soluble calcium salt to water soluble magnesiumsalt is 1-2:1-2, the weight ratio of water soluble magnesium salt togluconate is 1:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater, and the weight ratioof water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater, and the weight ratioof water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater, and the weight ratioof water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 1.5:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 1-15:1-8. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 1.5:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 3-10:1-5. In an embodiment, theweight ratio of water soluble calcium salt to water soluble magnesiumsalt is 1-2:1-2, the weight ratio of water soluble magnesium salt togluconate is 1.5:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 2:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 1-15:1-8. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 2:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 3-10:1-5. In an embodiment, theweight ratio of water soluble calcium salt to water soluble magnesiumsalt is 1-2:1-2, the weight ratio of water soluble magnesium salt togluconate is 2:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-12.5, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 1:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 1-19:1-13. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1:1, the weight ratio of water soluble magnesium saltto gluconate is 1:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 1-15:1-8. In an embodiment, the weightratio of water soluble calcium salt to water soluble magnesium salt is1:1, the weight ratio of water soluble magnesium salt to gluconate is1:1 or greater, and the weight ratio of water soluble calcium salt togluconate is 3-10:1-5. In an embodiment, the weight ratio of watersoluble calcium salt to water soluble magnesium salt is 1:1, the weightratio of water soluble magnesium salt to gluconate is 1:1 or greater,and the weight ratio of water soluble calcium salt to gluconate is3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater, and the weight ratioof water soluble calcium salt to gluconate is 1-19:1-13. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater, and the weight ratioof water soluble calcium salt to gluconate is 1-15:1-8. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater, and the weight ratioof water soluble calcium salt to gluconate is 3-10:1-5. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 11:1, the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater, and the weight ratioof water soluble calcium salt to gluconate is 3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 1.5:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 1-19:1-13. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1:1, the weight ratio of water soluble magnesium saltto gluconate is 1.5:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 1-15:1-8. In an embodiment, the weightratio of water soluble calcium salt to water soluble magnesium salt is1:1, the weight ratio of water soluble magnesium salt to gluconate is1.5:1 or greater, and the weight ratio of water soluble calcium salt togluconate is 3-10:1-5. In an embodiment, the weight ratio of watersoluble calcium salt to water soluble magnesium salt is 1:1, the weightratio of water soluble magnesium salt to gluconate is 1.5:1 or greater,and the weight ratio of water soluble calcium salt to gluconate is3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 2:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 1-19:1-13. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1:1, the weight ratio of water soluble magnesium saltto gluconate is 2:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 1-15:1-8. In an embodiment, the weightratio of water soluble calcium salt to water soluble magnesium salt is1:1, the weight ratio of water soluble magnesium salt to gluconate is2:1 or greater, and the weight ratio of water soluble calcium salt togluconate is 3-10:1-5. In an embodiment, the weight ratio of watersoluble calcium salt to water soluble magnesium salt is 1:1, the weightratio of water soluble magnesium salt to gluconate is 2:1 or greater,and the weight ratio of water soluble calcium salt to gluconate is3-8:2-4.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2 and the weight ratio of watersoluble calcium salt to gluconate is 4-7:1-3. In an embodiment, theweight ratio of water soluble calcium salt to water soluble magnesiumsalt is 1-2:1-2 and the weight ratio of water soluble calcium salt togluconate is 5-6:1-2. In an embodiment, the weight ratio of watersoluble calcium salt to water soluble magnesium salt is 1-2:1-2 and theweight ratio of water soluble calcium salt to gluconate is5.2-5.8:1.2-1.8. In an embodiment, the weight ratio of water solublecalcium salt to water soluble magnesium salt is 1-2:1-2 and the weightratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50 and the weight ratio ofwater soluble calcium salt to gluconate is 4-7:1-3. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-1.50:1-1.50 and the weight ratio of water solublecalcium salt to gluconate is 5-6:1-2. In an embodiment, the weight ratioof water soluble calcium salt to water soluble magnesium salt is1-1.50:1-1.50 and the weight ratio of water soluble calcium salt togluconate is 5.2-5.8:1.2-1.8. In an embodiment, the weight ratio ofwater soluble calcium salt to water soluble magnesium salt is1-1.50:1-1.50 and the weight ratio of water soluble calcium salt togluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25 and the weight ratio ofwater soluble calcium salt to gluconate is 4-7:1-3. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-1.25:1-1.25 and the weight ratio of water solublecalcium salt to gluconate is 5-6:1-2. In an embodiment, the weight ratioof water soluble calcium salt to water soluble magnesium salt is1-1.25:1-1.25 and the weight ratio of water soluble calcium salt togluconate is 5.2-5.8:1.2-1.8. In an embodiment, the weight ratio ofwater soluble calcium salt to water soluble magnesium salt is1-1.25:1-1.25 and the weight ratio of water soluble calcium salt togluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1 and the weight ratio of watersoluble calcium salt to gluconate is 4-7:1-3. In an embodiment, theweight ratio of water soluble calcium salt to water soluble magnesiumsalt is 1:1 and the weight ratio of water soluble calcium salt togluconate is 5-6:1-2. In an embodiment, the weight ratio of watersoluble calcium salt to water soluble magnesium salt is 1:1 and theweight ratio of water soluble calcium salt to gluconate is5.2-5.8:1.2-1.8. In an embodiment, the weight ratio of water solublecalcium salt to water soluble magnesium salt is 1:1 and the weight ratioof water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 1:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 4-7:1-3. In an embodiment, the weight ratioof water soluble magnesium salt to gluconate is 1:1 or greater and theweight ratio of water soluble calcium salt to gluconate is 5-6:1-2. Inan embodiment, the weight ratio of water soluble magnesium salt togluconate is 1:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 5.2-5.8:1.2-1.8. In an embodiment, theweight ratio of water soluble magnesium salt to gluconate is 1:1 orgreater and the weight ratio of water soluble calcium salt to gluconateis 11:3.

In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 1.25:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 4-7:1-3. In an embodiment, the weight ratioof water soluble magnesium salt to gluconate is 1.25:1 or greater andthe weight ratio of water soluble calcium salt to gluconate is 5-6:1-2.In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 1.25:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 5.2-5.8:1.2-1.8. In an embodiment, theweight ratio of water soluble magnesium salt to gluconate is 1.25:1 orgreater and the weight ratio of water soluble calcium salt to gluconateis 11:3.

In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 1.5:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 4-7:1-3. In an embodiment, the weight ratioof water soluble magnesium salt to gluconate is 1.5:1 or greater and theweight ratio of water soluble calcium salt to gluconate is 5-6:1-2. Inan embodiment, the weight ratio of water soluble magnesium salt togluconate is 1.5:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 5.2-5.8:1.2-1.8. In an embodiment, theweight ratio of water soluble magnesium salt to gluconate is 1.5:1 orgreater and the weight ratio of water soluble calcium salt to gluconateis 11:3.

In an embodiment, the weight ratio of water soluble magnesium salt togluconate is 2:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 4-7:1-3. In an embodiment, the weight ratioof water soluble magnesium salt to gluconate is 2:1 or greater and theweight ratio of water soluble calcium salt to gluconate is 5-6:1-2. Inan embodiment, the weight ratio of water soluble magnesium salt togluconate is 2:1 or greater and the weight ratio of water solublecalcium salt to gluconate is 5.2-5.8:1.2-1.8. In an embodiment, theweight ratio of water soluble magnesium salt to gluconate is 2:1 orgreater and the weight ratio of water soluble calcium salt to gluconateis 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 1:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 5-6:1-2. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 1:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 1:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater, and the weight ratioof water soluble calcium salt to gluconate is 5-6:1-2. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 1.25:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 1.25:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 1.5:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 5-6:1-2. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 1.5:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 1.5:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-2:1-2, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-2:1-2, the weight ratio of water solublemagnesium salt to gluconate is 2:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 5-6:1-2. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 2:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1-2:1-2, the weight ratio of water soluble magnesiumsalt to gluconate is 2:1 or greater, and the weight ratio of watersoluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5-6:1-2. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5-6:1-2. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5-6:1-2. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5-6:1-2. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.50:1-1.50, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5-6:1-2. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-12.5, the weight ratio of watersoluble magnesium salt to gluconate is 1:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5-6:1-2. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.25:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5-6:1-2. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 1.5:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 4-7:1-3. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5-6:1-2. In anembodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 5.2-5.8:1.2-1.8. Inan embodiment, the weight ratio of water soluble calcium salt to watersoluble magnesium salt is 1-1.25:1-1.25, the weight ratio of watersoluble magnesium salt to gluconate is 2:1 or greater, and the weightratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 1:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 4-7:1-3. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1:1, the weight ratio of water soluble magnesium saltto gluconate is 1:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 5-6:1-2. In an embodiment, the weight ratioof water soluble calcium salt to water soluble magnesium salt is 1:1,the weight ratio of water soluble magnesium salt to gluconate is 1:1 orgreater, and the weight ratio of water soluble calcium salt to gluconateis 5.2-5.8:1.2-1.8. In an embodiment, the weight ratio of water solublecalcium salt to water soluble magnesium salt is 1:1, the weight ratio ofwater soluble magnesium salt to gluconate is 1:1 or greater, and theweight ratio of water soluble calcium salt to gluconate is 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 1.25:1 or greater, and the weight ratioof water soluble calcium salt to gluconate is 4-7:1-3. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1:1, the weight ratio of water soluble magnesium saltto gluconate is 1.25:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 5-6:1-2. In an embodiment, the weight ratioof water soluble calcium salt to water soluble magnesium salt is 1:1,the weight ratio of water soluble magnesium salt to gluconate is 1.25:1or greater, and the weight ratio of water soluble calcium salt togluconate is 5.2-5.8:1.2-1.8. In an embodiment, the weight ratio ofwater soluble calcium salt to water soluble magnesium salt is 11:1, theweight ratio of water soluble magnesium salt to gluconate is 1.25:1 orgreater, and the weight ratio of water soluble calcium salt to gluconateis 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 1.5:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 4-7:1-3. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1:1, the weight ratio of water soluble magnesium saltto gluconate is 1.5:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 5-6:1-2. In an embodiment, the weight ratioof water soluble calcium salt to water soluble magnesium salt is 1:1,the weight ratio of water soluble magnesium salt to gluconate is 1.5:1or greater, and the weight ratio of water soluble calcium salt togluconate is 5.2-5.8:1.2-1.8. In an embodiment, the weight ratio ofwater soluble calcium salt to water soluble magnesium salt is 1:1, theweight ratio of water soluble magnesium salt to gluconate is 1.5:1 orgreater, and the weight ratio of water soluble calcium salt to gluconateis 11:3.

In an embodiment, the weight ratio of water soluble calcium salt towater soluble magnesium salt is 1:1, the weight ratio of water solublemagnesium salt to gluconate is 2:1 or greater, and the weight ratio ofwater soluble calcium salt to gluconate is 4-7:1-3. In an embodiment,the weight ratio of water soluble calcium salt to water solublemagnesium salt is 1:1, the weight ratio of water soluble magnesium saltto gluconate is 2:1 or greater, and the weight ratio of water solublecalcium salt to gluconate is 5-6:1-2. In an embodiment, the weight ratioof water soluble calcium salt to water soluble magnesium salt is 1:1,the weight ratio of water soluble magnesium salt to gluconate is 2:1 orgreater, and the weight ratio of water soluble calcium salt to gluconateis 5.2-5.8:1.2-1.8. In an embodiment, the weight ratio of water solublecalcium salt to water soluble magnesium salt is 1:1, the weight ratio ofwater soluble magnesium salt to gluconate is 2:1 or greater, and theweight ratio of water soluble calcium salt to gluconate is 11:3.

The present corrosion inhibitor can include 1 wt-% gluconate and alsoinclude amounts of water soluble magnesium salt and water solublecalcium salt to provide an embodiment of these ratios. The presentcorrosion inhibitor can include 2 wt-% gluconate and also includeamounts of water soluble magnesium salt and water soluble calcium saltto provide an embodiment of these ratios. The present corrosioninhibitor can include 3 wt-% gluconate and also include amounts of watersoluble magnesium salt and water soluble calcium salt to provide anembodiment of these ratios. The present corrosion inhibitor can include4 wt-% gluconate and also include amounts of water soluble magnesiumsalt and water soluble calcium salt to provide an embodiment of theseratios. The present corrosion inhibitor can include 5 wt-% gluconate andalso include amounts of water soluble magnesium salt and water solublecalcium salt to provide an embodiment of these ratios. The presentcorrosion inhibitor can include 6 wt-% gluconate and also includeamounts of water soluble magnesium salt and water soluble calcium saltto provide an embodiment of these ratios. The present corrosioninhibitor can include 7 wt-% gluconate and also include amounts of watersoluble magnesium salt and water soluble calcium salt to provide anembodiment of these ratios. The present corrosion inhibitor can include8 wt-% gluconate and also include amounts of water soluble magnesiumsalt and water soluble calcium salt to provide an embodiment of theseratios. The present corrosion inhibitor can include 9 wt-% gluconate andalso include amounts of water soluble magnesium salt and water solublecalcium salt to provide an embodiment of these ratios.

The present corrosion inhibitor can include 10 wt-% gluconate and alsoinclude amounts of water soluble magnesium salt and water solublecalcium salt to provide an embodiment of these ratios. The presentcorrosion inhibitor can include 11 wt-% gluconate and also includeamounts of water soluble magnesium salt and water soluble calcium saltto provide an embodiment of these ratios. The present corrosioninhibitor can include 12 wt-% gluconate and also include amounts ofwater soluble magnesium salt and water soluble calcium salt to providean embodiment of these ratios. The present corrosion inhibitor caninclude 13 wt-% gluconate and also include amounts of water solublemagnesium salt and water soluble calcium salt to provide an embodimentof these ratios. The present corrosion inhibitor can include 14 wt-%gluconate and also include amounts of water soluble magnesium salt andwater soluble calcium salt to provide an embodiment of these ratios. Thepresent corrosion inhibitor can include 15 wt-% gluconate and alsoinclude amounts of water soluble magnesium salt and water solublecalcium salt to provide an embodiment of these ratios. The presentcorrosion inhibitor can include 16 wt-% gluconate and also includeamounts of water soluble magnesium salt and water soluble calcium saltto provide an embodiment of these ratios. The present corrosioninhibitor can include 17 wt-% gluconate and also include amounts ofwater soluble magnesium salt and water soluble calcium salt to providean embodiment of these ratios. The present corrosion inhibitor caninclude 18 wt-% gluconate and also include amounts of water solublemagnesium salt and water soluble calcium salt to provide an embodimentof these ratios. The present corrosion inhibitor can include 19 wt-%gluconate and also include amounts of water soluble magnesium salt andwater soluble calcium salt to provide an embodiment of these ratios.

The present corrosion inhibitor can include 20 wt-% gluconate and alsoinclude amounts of water soluble magnesium salt and water solublecalcium salt to provide an embodiment of these ratios. The presentcorrosion inhibitor can include 21 wt-% gluconate and also includeamounts of water soluble magnesium salt and water soluble calcium saltto provide an embodiment of these ratios. The present corrosioninhibitor can include 22 wt-% gluconate and also include amounts ofwater soluble magnesium salt and water soluble calcium salt to providean embodiment of these ratios. The present corrosion inhibitor caninclude 23 wt-% gluconate and also include amounts of water solublemagnesium salt and water soluble calcium salt to provide an embodimentof these ratios. The present corrosion inhibitor can include 24 wt-%gluconate and also include amounts of water soluble magnesium salt andwater soluble calcium salt to provide an embodiment of these ratios. Thepresent corrosion inhibitor can include 25 wt-% gluconate and alsoinclude amounts of water soluble magnesium salt and water solublecalcium salt to provide an embodiment of these ratios.

The present invention may be better understood with reference to thefollowing examples. These examples are intended to be representative ofspecific embodiments of the invention, and are not intended as limitingthe scope of the invention.

EXAMPLES Example 1 Magnesium Salt, Calcium Salt and GluconateSynergistically Reduced Corrosion of Aluminum

Compositions of hardness ions (e.g., calcium and magnesium ions) andgluconate synergistically reduced corrosion of aluminum.

Materials and Methods

Coupons of aluminum 6061 (1″×3″× 1/16″) were immersed in a series ofcompositions having a total of about 400 ppm of magnesium chloride,calcium chloride, and sodium gluconate. Table 1, below, shows the actualamounts of magnesium chloride, calcium chloride and gluconate in eachcomposition. The compositions also included about 400 ppm of a 50/50blend of sodium carbonate/sodium hydroxide to provide alkalinity as asource of corrosion. The compositions were prepared by mixing thecomponents of the compositions together and stirring until a homogeneousmixture was formed.

The compositions were incubated for 24 hours at 160° F. The amount ofaluminum dissolved into solution from the aluminum coupons by thealkalinity was determined. The amount of aluminum present in solutionreflected the rate of aluminum corrosion and etching.

Results

Table 1 shows the component compositions and amount of aluminum removedfrom the aluminum coupons.

TABLE 1 Sodium MgCl₂ CaCl₂ Gluconate Aluminum Dissolved Composition(ppm) (ppm) (ppm) Into Solution (ppm) 1 0 400 0 38.2 2 100 300 0 30.4 3200 200 0 62.1 4 300 100 0 26.5 5 400 0 0 29.9 6 300 0 100 31.5 7 200 0200 41.2 8 100 0 300 53.9 9 0 0 400 50.6 10 0 100 300 48.3 11 0 200 20049.5 12 0 300 100 52.3 13 100 200 100 31 14 200 100 100 27.6 15 100 100200 37.5 16 50 300 50 33.3 17 300 50 50 30.3 18 50 50 300 36 19 133 133132 27.2

FIG. 1 shows a ternary graph illustrating the reduced corrosion ofaluminum as a function of the concentrations of magnesium, calcium, andgluconate. This ternary graph was produced by entering the data in Table1 into a statistics program, Design Expert, version 6.0.11, availablefrom Stat-Ease, Minneapolis, Minn. The program analyzed the raw data tofind a trend and developed the following equation, Equation 1:

Al in soln (ppm)=0.099653*CaCl2+0.072577*MgCl2+0.12246*Nagluconate−1.96236E-004*CaCl2*MgCl2+1.35722E-004*CaCl2*Nagluconate+7.92997E-005*MgCl2*Na gluconate−4.61845E-006*CaCl2*MgCl2*Nagluconate

Equation 1 was then plotted to create the ternary graph depicted in FIG.1.

Discussion

FIG. 1 shows that water soluble magnesium salt, water soluble calciumsalt, and gluconate reduced aluminum corrosion at selected synergisticratios and beyond. Synergistic ratios include:

Synergistic Weight Ratios Water soluble calcium salt to 1-2:1-21-1.50:1-1.50 1-1.25:1-1.25 1:1 water soluble magnesium salt Watersoluble magnesium salt 1:1 or 1.25:1 or 1.5:1 or 2:1 or to gluconategreater greater greater greater Water soluble calcium salt to 1-19:1-131-15:1-8 3-10:1-5 3-8:2-4 gluconate

Example 2 Magnesium Salt, Calcium Salt and Gluconate Reduced Corrosionof Aluminum and Galvanized Steel Better Than Other Corrosion Inhibitors

Corrosion inhibitors containing hardness ions (e.g., Ca²⁺ and Mg²⁺) andgluconate were compared to conventional corrosion inhibitors and foundto provide superior protection of two soft metals, aluminum andgalvanized steel.

Materials and Methods

Coupons were cut from aluminum (1100 grade) and from galvanized steel toa size of 1″×3″. The coupons were cleaned, weighed, and contacted withan alkaline cleaning composition by immersion or foaming. The aluminumcoupons were immersed for 8 hours, the galvanized steel coupons for 24hours. In a first foaming method, the coupons were suspended above afoaming alkaline cleaning composition, the composition was foamed, andthe coupons remained in the foam for 8 hours (Glewwe foaming test). In asecond foaming method, the coupons were suspended in a foaming station.The coupons were subjected to repeated cycles of contacting with afoaming alkaline cleaning composition, rinsing, and drying over 24hours. After contacting with the cleaning composition, the coupons arecleaned and weighed again.

The alkaline cleaning compositions were:

wt-% Ingredient A B Alkali Metal Hydroxide 16 11 Builder 4.1 5Surfactant 6 25 Water 67 32 Chlorine Source 0.1 0.1 Corrosion Inhibitorv v Use Dilution 2.5 1.4

The corrosion inhibitors tested were: 500 ppm amine borate corrosioninhibitor; 500 ppm amine borate plus 500 ppm ester of oxid petro; 700ppm Crodasinic 0; 175 ppm potassium silicate plus 1400 ppm boric acid;425 ppm Berol 425; 900 ppm sodium nitrate; 400 ppm PEG-600 Diacid; 2000ppm PEG-600; calcium magnesium gluconate composition #1 (inverted, 133ppm, 229 ppm, 57 ppm); calcium magnesium gluconate composition #2 (344ppm, 80 ppm, 57 ppm); calcium chloride, magnesium chloride, silicate(186 ppm, 80 ppm, 200 ppm); Acusol, sodium sulfite, sodium gluconate(325 ppm, 1130 ppm, 2828 ppm); calcium chloride, magnesium chloride,aminopropylsilanetriol (186 ppm, 80 ppm, 200 ppm); 200 ppmaminopropylsilanetriol (APST); aminopropylsilanetriol pretreatment; andmineral oil pretreatment.

Results

The amount of corrosion in mil per year is reported in the graphs below.These graphs show that the calcium magnesium gluconate composition #1(inverted, 133 ppm, 229 ppm, 57 ppm) was superior to the other corrosioninhibitors.

TABLE 2 Immersion Test Aluminum Corrosion Using Composition A andVarious Corrosion Inhibitors Corrosion Corrosion Inhibitor (MPY) None1366.44 Amine Borate with Oil 519.04 Amine Borate 572.16 Crodasinic O609.69 Potassium Silicate + Boric Acid 221.87 Sodium Nitrite 799.86 PEG600 611.34 MgCl₂ CaCl₂ Silicate 426.36 MgCl₂ CaCl₂ Gluconate 586.23MgCl₂ CaCl₂ APST 345.86 Berol 275 657.23 Pretreat with APST 635.68Pretreat with WM Oil 750.03 PEG 600 Diacid 644.05 APST 556.69 Acusol,Sulfite, Gluconate 734.06 Inverted MgCl₂ CaCl₂ Gluconate 180

TABLE 3 Immersion Test Aluminum Corrosion Using Compositions A and BIncluding Selected Corrosion Inhibitors Corrosion (MPY) CorrosionInhibitor A B None 1366.44 702.98 Amine Borate with Oil 519.04 604.1Amine Borate 572.16 599.04 Crodasinic O 609.69 402.91 PotassiumSilicate + Boric Acid 221.87 123.10 Na Nitrite 799.86 418.38 PEG 600611.34 455.40 MgCl₂ CaCl₂ Silicate 426.3 103.90 MgCl₂ CaCl₂ Gluconate586.23 128.05 MgCl₂ CaCl₂ APST 345.86 86.84 APST 556.69 295.40 Acusol,Sulfite, Gluconate 734.00 435.62

TABLE 4 Glewwe Foam Test Aluminum Corrosion Using Composition A andVarious Corrosion Inhibitors Corrosion Corrosion Inhibitor (MPY) None392.86 Amine Borate with Oil 371.85 Amine Borate 572.41 Crodasinic O552.26 Potassium Silicate + Boric Acid 133.25 Sodium Nitrite 336.98 PEG600 831.55 MgCl₂, CaCl₂ Silicate 61.49 MgCl₂ CaCl₂ Gluconate 101.17MgCl₂ CaCl₂ APST 43.23 Berol 275 194.99 PEG Diacid 240.88 APST 243.29Acusol, Sulfite, Gluconate 125.77 Inverted MgCl₂ CaCl₂ Gluconate 89

TABLE 5 Glewwe Foam Test Aluminum Corrosion Using Compositions A and BIncluding Selected Corrosion Inhibitors Corrosion (MPY) CorrosionInhibitor A B None 392.86 286.21 Amine Borate with Oil 371.85 372.61Amine Borate 572.41 158.98 Crodasinic O 552.26 240.63 PotassiumSilicate + Boric Acid 133.25 28.78 Na Nitrite 339.9 267.89 PEG 600831.55 218.82 MgCl₂, CaCl₂, Silicate 61.49 115.40 MgCl₂, CaCl₂,Gluconate 101.17 127.03 MgCl₂, CaCl₂, APST 43.23 117.27 APST 243.29197.27 Acusol, Sulfite, Gluconate 125.77 281.96

TABLE 6 Foam Station Test Aluminum Corrosion Using Compositions A and BIncluding Selected Corrosion Inhibitors Corrosion (MPY) CorrosionInhibitor A B None 23.58 30.55 Mg/Ca/Gluconate 10.57 19.44 Mg/Ca/Si11.03 10.1 Ksil/Boric Acid 0.85 0.3 Mg/Ca/APST 8.24 12.17

TABLE 7 Immersion Test Steel Corrosion Using Composition A and VariousCorrosion Inhibitors Corrosion Corrosion Inhibitor (MPY) Control 0.96CaCl₂ MgCl₂ Na Gluconate 1.33 CaCl₂ MgCl₂ Silicate 1.21 PotassiumSilicate + Boric 4.15 Acid PEG-600 0.97 CaCl₂ MgCl₂ APST 0.92 Na Nitrite0.93 Amine Borate with Oil 1.34 Amine Borate 0.92 Crodasinic O 0.93Berol 725 0.96 APST 1.14 Acusol, sulfite, gluconate 2.66 PEG-600 Diacid0.43 Inverted CaCl₂ MgCl₂ Na 2.3 Gluconate

TABLE 8 Immersion Test Steel Corrosion Using Composition B and VariousCorrosion Inhibitors Corrosion Corrosion Inhibitor (MPY) Control 0.99CaCl₂ MgCl₂ Na Gluconate 3.19 CaCl₂ MgCl₂ Silicate 0.59 PotassiumSilicate + Boric Acid 3.96 PEG-600 0.92 CaCl₂ MgCl₂ APST 1.04 Na Nitrite0.78 Amine Borate with Oil 2.98 Amine Borate 1.85 Crodasinic O 1.02Berol 725 0.78 APST 1.19 Acusol, sulfite, gluconate 5.88

TABLE 9 Foam Station Test Aluminum Corrosion Using Compositions A and BIncluding Selected Corrosion Inhibitors Corrosion (MPY) CorrosionInhibitor A B Control 3.5 7.50 MgCl₂ CaCl₂ Gluconate 2.58 7.89 MgCl₂CaCl₂ Silicate 2.56 7.03 Potassium Silicate + Boric Acid 2.2 5.41 CaCl₂MgCl₂ APST 2.03 8.73 PEG 600 3.46

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes a mixture oftwo or more compounds. It should also be noted that the term “or” isgenerally employed in its sense including “and/or” unless the contentclearly dictates otherwise.

It should also be noted that, as used in this specification and theappended claims, the term “configured” describes a system, apparatus, orother structure that is constructed or configured to perform aparticular task or adopt a particular configuration. The term“configured” can be used interchangeably with other similar phrases suchas arranged and configured, constructed and arranged, adapted andconfigured, adapted, constructed, manufactured and arranged, and thelike.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated by reference.

The invention has been described with reference to various specific andpreferred embodiments and techniques. However, it should be understoodthat many variations and modifications may be made while remainingwithin the spirit and scope of the invention.

1. A corrosion inhibiting composition comprising: about 1 to about 98wt-% water soluble calcium salt and water soluble magnesium salt; andabout 1 to about 60 wt-% gluconate; wherein the weight ratio of watersoluble magnesium salt to water soluble calcium salt is about 1-2:1-2;the weight ratio of water soluble magnesium salt to gluconate is greaterthan 1:1; and the weight ratio of water soluble calcium salt togluconate is about 1-19:1:13.
 2. The composition of claim 1, wherein theweight ratio of water soluble magnesium salt to water soluble calciumsalt is about 1-1.5:1-1.5; the weight ratio of water soluble magnesiumsalt to gluconate is greater than 1.25:1; and the weight ratio of watersoluble calcium salt to gluconate is about 1-15:1-8.
 3. The compositionof claim 1, wherein the weight ratio of water soluble magnesium salt towater soluble calcium salt is about 1-1.25:1-1.25; the weight ratio ofwater soluble magnesium salt to gluconate is greater than 1.5:1; and theweight ratio of water soluble calcium salt to gluconate is about3-10:1-5.
 4. The composition of claim 1, wherein the weight ratio ofwater soluble magnesium salt to water soluble calcium salt is about 1:1;the weight ratio of water soluble magnesium salt to gluconate is greaterthan 2:1; and the weight ratio of water soluble calcium salt togluconate is about 3-8:2-4.
 5. The composition of claim 1, wherein thegluconate is selected from the group consisting of sodium gluconate,lithium gluconate, potassium gluconate or a mixture thereof.
 6. Thecomposition of claim 1, wherein the water soluble magnesium salt isselected from the group consisting of magnesium acetate, magnesiumbenzoate, magnesium bromide, magnesium bromate, magnesium chlorate,magnesium chloride, magnesium chromate, magnesium citrate, magnesiumformate, magnesium hexafluorosilicate, magnesium iodate, magnesiumiodide, magnesium lactate, magnesium molybdate, magnesium nitrate,magnesium perchlorate, magnesium phosphinate, magnesium salicylate,magnesium sulfate, magnesium sulfite, magnesium thiosulfate, a hydratethereof, and a mixture thereof.
 7. The composition of claim 1, whereinthe water soluble calcium salt is selected from the group consisting ofcalcium acetate, calcium benzoate, calcium bromate, calcium bromide,calcium chlorate, calcium chloride, calcium chromate, calcium dihydrogenphosphate, calcium dithionate, calcium formate, calcium gluconate,calcium glycerophosphate, calcium hydrogen sulfide, calcium iodide,calcium lactate, calcium metasilicate, calcium nitrate, calcium nitrite,calcium pantothenate, calcium perchlorate, calcium permanganate, calciumphosphate, calcium phosphinate, calcium salicylate, calcium succinate, ahydrate thereof, and a mixture thereof.
 8. The composition of claim 1,comprising less than about 0.5 wt-% zinc-containing compounds.
 9. Thecomposition of claim 1, comprising less than about 0.5 wt-%aluminum-containing compounds.
 10. The composition of claim 1,comprising less than about 0.5 wt-% phosphorous-containing compounds.11. A detergent for warewashing or automatic dishwashing, the detergentcomprising source of alkalinity and about 0.01 to about 20 wt-%corrosion inhibitor; the corrosion inhibitor comprising: about 1 toabout 98 wt-% water soluble calcium salt and water soluble magnesiumsalt; and about 1 to about 60 wt-% gluconate; wherein the weight ratioof water soluble magnesium salt to water soluble calcium salt is about1-2:1-2; the weight ratio of water soluble magnesium salt to gluconateis greater than 1:1; and the weight ratio of water soluble calcium saltto gluconate is about 1-19:1:13.
 12. The detergent of claim 11,comprising about 0.1 to about 10 wt-% corrosion inhibitor.
 13. Thedetergent of claim 11, further comprising surfactant.
 14. The detergentof claim 11, wherein the weight ratio of water soluble magnesium salt towater soluble calcium salt is about 1-1.5:1-1.5; the weight ratio ofwater soluble magnesium salt to gluconate is greater than 1.25:1; andthe weight ratio of water soluble calcium salt to gluconate is about1-15:1-8.
 15. The detergent of claim 11, wherein the weight ratio ofwater soluble magnesium salt to water soluble calcium salt is about1-1.25:1-1.25; the weight ratio of water soluble magnesium salt togluconate is greater than 1.5:1; and the weight ratio of water solublecalcium salt to gluconate is about 3-10:1-5.
 16. The detergent of claim11, wherein the weight ratio of water soluble magnesium salt to watersoluble calcium salt is about 1:1; the weight ratio of water solublemagnesium salt to gluconate is greater than 2:1; and the weight ratio ofwater soluble calcium salt to gluconate is about 3-8:2-4.
 17. Thedetergent of claim 11, wherein the gluconate is selected from the groupconsisting of sodium gluconate, lithium gluconate, potassium gluconateor a mixture thereof.
 18. The detergent of claim 11, wherein the watersoluble magnesium salt is selected from the group consisting ofmagnesium acetate, magnesium benzoate, magnesium bromide, magnesiumbromate, magnesium chlorate, magnesium chloride, magnesium chromate,magnesium citrate, magnesium formate, magnesium hexafluorosilicate,magnesium iodate, magnesium iodide, magnesium lactate, magnesiummolybdate, magnesium nitrate, magnesium perchlorate, magnesiumphosphinate, magnesium salicylate, magnesium sulfate, magnesium sulfite,magnesium thiosulfate, a hydrate thereof, and a mixture thereof.
 19. Thedetergent of claim 11, wherein the water soluble calcium salt isselected from the group consisting of calcium acetate, calcium benzoate,calcium bromate, calcium bromide, calcium chlorate, calcium chloride,calcium chromate, calcium dihydrogen phosphate, calcium dithionate,calcium formate, calcium gluconate, calcium glycerophosphate, calciumhydrogen sulfide, calcium iodide, calcium lactate, calcium metasilicate,calcium nitrate, calcium nitrite, calcium pantothenate, calciumperchlorate, calcium permanganate, calcium phosphate, calciumphosphinate, calcium salicylate, calcium succinate, a hydrate thereof,and a mixture thereof.
 20. The detergent of claim 11, comprising lessthan about 0.5 wt-% zinc-containing compounds.
 21. The detergent ofclaim 11, comprising less than about 0.5 wt-% aluminum-containingcompounds.
 22. The detergent of claim 11, comprising less than about 0.5wt-% phosphorous-containing compounds.
 23. A hard surface cleanercomprising surfactant and about 0.01 to about 20 wt-% corrosioninhibitor; the corrosion inhibitor comprising: about 1 to about 98 wt-%water soluble calcium salt and water soluble magnesium salt; and about 1to about 60 wt-% gluconate; wherein the weight ratio of water solublemagnesium salt to water soluble calcium salt is about 1-2:1-2; theweight ratio of water soluble magnesium salt to gluconate is greaterthan 1:1; and the weight ratio of water soluble calcium salt togluconate is about 1-19:1:13.
 24. The cleaner of claim 23, comprisingabout 0.1 to about 10 wt-% corrosion inhibitor.
 25. The cleaner of claim23, further comprising an alkalinity source.
 26. The cleaner of claim23, comprising about 0.1 to about 10 wt-% corrosion inhibitor.
 27. Thecleaner of claim 23, further comprising a surfactant.
 28. The cleaner ofclaim 23, wherein the weight ratio of water soluble magnesium salt towater soluble calcium salt is about 1-1.5:1-1.5; the weight ratio ofwater soluble magnesium salt to gluconate is greater than 1.25:1; andthe weight ratio of water soluble calcium salt to gluconate is about1-15:1-8.
 29. The cleaner of claim 23, wherein the weight ratio of watersoluble magnesium salt to water soluble calcium salt is about1-1.25:1-1.25; the weight ratio of water soluble magnesium salt togluconate is greater than 1.5:1; and the weight ratio of water solublecalcium salt to gluconate is about 3-10:1-5.
 30. The cleaner of claim23, wherein the weight ratio of water soluble magnesium salt to watersoluble calcium salt is about 1:1; the weight ratio of water solublemagnesium salt to gluconate is greater than 2:1; and the weight ratio ofwater soluble calcium salt to gluconate is about 3-8:2-4.
 31. Thecleaner of claim 23, wherein the gluconate is selected from the groupconsisting of sodium gluconate, lithium gluconate, potassium gluconateor a mixture thereof.
 32. The cleaner of claim 23, wherein the watersoluble magnesium salt is selected from the group consisting ofmagnesium acetate, magnesium benzoate, magnesium bromide, magnesiumbromate, magnesium chlorate, magnesium chloride, magnesium chromate,magnesium citrate, magnesium formate, magnesium hexafluorosilicate,magnesium iodate, magnesium iodide, magnesium lactate, magnesiummolybdate, magnesium nitrate, magnesium perchlorate, magnesiumphosphinate, magnesium salicylate, magnesium sulfate, magnesium sulfite,magnesium thiosulfate, a hydrate thereof, and a mixture thereof.
 33. Thecleaner of claim 23, wherein the water soluble calcium salt is selectedfrom the group consisting of calcium acetate, calcium benzoate, calciumbromate, calcium bromide, calcium chlorate, calcium chloride, calciumchromate, calcium dihydrogen phosphate, calcium dithionate, calciumformate, calcium gluconate, calcium glycerophosphate, calcium hydrogensulfide, calcium iodide, calcium lactate, calcium metasilicate, calciumnitrate, calcium nitrite, calcium pantothenate, calcium perchlorate,calcium permanganate, calcium phosphate, calcium phosphinate, calciumsalicylate, calcium succinate, a hydrate thereof, and a mixture thereof.34. The cleaner of claim 23, comprising less than about 0.5 wt-%zinc-containing compounds.
 35. The cleaner of claim 23, comprising lessthan about 0.5 wt-% aluminum-containing compounds.
 36. The cleaner ofclaim 23, comprising less than about 0.5 wt-% phosphorous-containingcompounds.
 37. A method of inhibiting corrosion during cleaning, themethod comprising: providing a corrosion inhibitor comprising: about 1to about 98 wt-% water soluble calcium salt and water soluble magnesiumsalt; and about 1 to about 60 wt-% gluconate; wherein the weight ratioof water soluble magnesium salt to water soluble calcium salt is about1-2:1-2; the weight ratio of water soluble magnesium salt to gluconateis greater than 1:1; and the weight ratio of water soluble calcium saltto gluconate is about 1-19:1:13; preparing an aqueous use composition ofthe corrosion inhibitor; and contacting an object in need of cleaningwith the aqueous use composition.
 38. A method of washing ware, themethod comprising: providing a detergent for warewashing or automaticdishwashing, the detergent comprising source of alkalinity and about0.01 to about 20 wt-% corrosion inhibitor; the corrosion inhibitorcomprising: about 1 to about 98 wt-% water soluble calcium salt andwater soluble magnesium salt; and about 1 to about 60 wt-% gluconate;wherein the weight ratio of water soluble magnesium salt to watersoluble calcium salt is about 1-2:1-2; the weight ratio of water solublemagnesium salt to gluconate is greater than 1:1; and the weight ratio ofwater soluble calcium salt to gluconate is about 1-19:1:13; preparing anaqueous use composition of the detergent for warewashing or automaticdishwashing; and contacting the ware with the aqueous use composition.39. A method of cleaning a hard surface, the method comprising:providing a hard surface cleaner comprising surfactant and about 0.01 toabout 20 wt-% corrosion inhibitor; the corrosion inhibitor comprising:about 1 to about 98 wt-% water soluble calcium salt and water solublemagnesium salt; and about 1 to about 60 wt-% gluconate; wherein theweight ratio of water soluble magnesium salt to water soluble calciumsalt is about 1-2:1-2; the weight ratio of water soluble magnesium saltto gluconate is greater than 1:1; and the weight ratio of water solublecalcium salt to gluconate is about 1-19:1:13; preparing an aqueous usecomposition of the hard surface cleaner; and contacting the hard surfacewith the aqueous use composition.
 40. A method of corrosion control in afood or beverage processing facility, the method comprising: providingan alkaline cleaner or a corrosion control composition comprising about0.01 to about 100 wt-% corrosion inhibitor; the corrosion inhibitorcomprising: about 1 to about 98 wt-% water soluble calcium salt andwater soluble magnesium salt; and about 1 to about 60 wt-% gluconate;wherein the weight ratio of water soluble magnesium salt to watersoluble calcium salt is about 1-2:1-2; the weight ratio of water solublemagnesium salt to gluconate is greater than 1:1; and the weight ratio ofwater soluble calcium salt to gluconate is about 1-19:1:13; preparing anaqueous use composition of the alkaline cleaner; introducing the aqueoususe composition into the process facilities at a temperature in therange of about 4° C. to 60° C.; holding the aqueous use composition in acontainer or circulating the aqueous use composition throughout thesystem for a time sufficient to clean; and draining the aqueous usecomposition from the container or system.
 41. The composition of claim23, comprising about 0.05 wt. % to about 15 wt. % surfactant.
 42. Thecomposition of claim 23, wherein the surfactant is selected from thegroup consisting of anionic surfactant, nonionic surfactant, cationicsurfactant, zwitterionic surfactant, and a mixture thereof.
 43. Thecomposition of claim 11, wherein the alkaline source is selected fromthe group consisting of alkali metal carbonate, alkali metal hydroxide,and mixture thereof.
 44. The composition of claim 11, wherein thealkaline source is selected from the group consisting of sodiumcarbonate, potassium carbonate, sodium bicarbonate, potassiumbicarbonate, sodium sesquicarbonate, potassium sesquicarbonate, andmixture thereof.
 45. The composition of claim 11, wherein the alkalinesource is selected from the group consisting of sodium hydroxide,potassium hydroxide, and mixture thereof.